TW201629111A - Functionalized elastomeric polymer compositions, their preparation methods and crosslinked rubber compositions thereof - Google Patents

Abstract

The invention relates to an elastomeric polymer composition and its preparation. The polymer composition comprises in combination a single terminally modified conjugated diene (co)polymer and a dual terminally modified conjugated diene (co)polymer. The polymer composition is useful in the preparation of a vulcanized and, thus, crosslinked elastomeric composition having relatively low hysteresis loss, good grip and low heat build-up properties.

Description

Functionalized elastomeric polymer composition, preparation method thereof and crosslinked rubber composition thereof

This invention relates to elastomeric polymer compositions and their preparation. The polymer composition comprises a single terminal modified conjugated diene (co)polymer and a dual terminal modified conjugated diene (co)polymer in a combined form. The polymer composition is suitable for use in the preparation of vulcanized and thus crosslinked elastomeric compositions having relatively low hysteresis loss, good grip and low heat build-up characteristics. These compositions are suitable for a wide variety of applications, including low heat buildup and fuel consumption, as well as other desirable physical and chemical properties (eg good wet grip, ice grip, abrasion resistance, tensile strength, and excellent processability). Sexually balanced tire tread.

The hysteresis energy loss of vulcanized rubber is generally related to the number of free polymer chain ends. For example, polymers having a high molecular weight exhibit reduced end group weight content and have reduced hysteresis loss, and result in reduced processability of the rubber compound. Functionalizing the chain ends with polar groups suitable for interaction with the filler produces a reduced amount of free chain ends and generally reduces hysteresis. However, a large number of chain end-filler interactions result in significantly reduced processability of the compound.

The elastomeric polymer obtained by the anionic polymerization process mainly contains a linear polymer chain. Highly linear elastomeric polymer chains exhibit high solution viscosity and cold flow characteristics. To overcome these drawbacks, coupling methods have been applied to produce at least partial branching of the polymer chains. A commonly used coupling agent is a halide or alkoxide compound of divinylbenzene, tin or bismuth. However, branched or star polymers produced by such coupling reactions typically exhibit increased hysteresis loss or reduced abrasion resistance.

WO 2007/047943 describes the use of decane sulfide ω chain end modifiers to produce A chain end modified elastomeric polymer that is used as a component in a vulcanized elastomeric polymer composition or tire tread.

According to WO 2007/047943, a decane sulfide compound is reacted with an anion-initiating living polymer to produce a "chain-end modified" polymer which is subsequently blended with a filler, a vulcanizing agent, a promoter or an oil filler. A vulcanized elastomeric polymer composition with low hysteresis loss is produced.

The vulcanized elastomeric polymer compositions are described as exhibiting lower tan delta values at 60 ° C, especially as compared to compounds based on corresponding unmodified polymers, without adversely affecting the tan delta value at 0 ° C and Processing characteristics, such as compound Mooney values. The lower tan δ value at 60 ° C corresponds to lower rolling resistance, while the higher tan δ at 0 ° C corresponds to the improved wet grip of the tire. Exemplary cured polymer formulations have been shown to result in a decrease in tan δ at 60 ° C and a heat buildup value but equal tan δ values at 0 °C. It is described as being suitable for use in the preparation of tire treads having lower rolling resistance but maintaining good wet grip characteristics. Although the cured rubber hysteresis characteristics can be significantly improved by applying the technique described in WO 2007/047943, the effect of this technique is attributed to the fact that only one polymer chain end can be functionalized by using the described modifier compound. Limited. Therefore, it is necessary to effectively modify the second polymer chain end.

EP 2 518 104 discloses rubber compositions for tire applications comprising a polymer based on a diene monomer and cerium oxide. The diene polymer is prepared from an initiator to produce an active polymer chain having two living polymer ends.

There is a need for a modification process and the resulting polymer, including modified polymers, to impart a good balance of dynamic properties to the crosslinked rubber compound containing cerium oxide, such as low hysteresis loss and high abrasion resistance, which corresponds to the tire High wet grip, low rolling resistance and high wear resistance, and maintain acceptable or improved processability. Also, it may be desirable to provide a polymer that exhibits good processability: (a) during the manufacturing process of the polymer itself, such as due to low viscosity during solvent and moisture removal processes, and (b) further processing The procedure (such as the preparation and processing of a rubber formulation filled with cerium oxide). These needs have been met by the following inventions.

In a first aspect, the present invention provides a polymer composition comprising, in its general embodiment (also referred to herein as "first polymer composition"), according to Formulas 1 and 2 below. Modified polymer: A ¹ -P ¹ -A ² Formula 1

A ³ -P ² type 2

Wherein P ¹ and P ² are each independently a polymer chain obtainable by anionic polymerization of one or more polymerizable monomers selected from the group consisting of conjugated dienes and aromatic vinyl compounds, wherein each polymer chain P ¹ and P ² contains at least 40% by weight of the repeating unit obtained by the polymerization of the conjugated dienes, and wherein at least the anionic polymerization of the polymer chain P ¹ is carried out in the presence of a compound of the following formula 9a:

Wherein each R ^{31 is} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl, and (C ₇ -C ₁₈ )aralkyl; each R ³² , R ³³ and R ³⁴ Independently selected from the group consisting of hydrogen, (C ₁ -C ₁₈ )alkyl and (C ₁ -C ₁₈ )alkoxy; each R ^{41 is} independently selected from (C ₁ -C ₁₀₀ )alkyl and (C ₂ -C ₁₀₀ Alkenyl, wherein each R ^{41 is} optionally substituted with one to three (C ₆ -C ₁₂ ) aryl groups and optionally via up to 25 monomer units selected from the group consisting of conjugated dienes and aromatic vinyl compounds The oligomer chain is bonded to the skeleton of the formula 9a, such as 1,3-butadiene and isoprene, and the aromatic vinyl compounds are especially styrene and divinylbenzene. Each M ^{2 is} independently selected from the group consisting of lithium, sodium, and potassium; and k, l, and q are independently selected from the integers of 0, ¹ , ^2, and ³ ; and A ¹ , A ^{2 ,} and A ^{3 are} independently selected from the following formula 3 To Equation 8:

Wherein each R ^{1 is} independently selected from (C ₁ -C ₁₆ )alkyl; each R ^{2 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C) ₁₈ )Aralkyl; a and b are independently selected from the integers of 0, 1 and 2, wherein a+b=2; R ^{3 is} independently selected from divalent (C ₁ -C ₁₆ )alkyl, divalent ( C ₆ -C ₁₈ ) aryl, divalent (C ₇ -C ₁₈ ) aralkyl and -R ⁴ -OR ⁵ -, wherein R ⁴ and R ^{5 are} independently selected from divalent (C ₁ -C ₆ ) alkane And Z are independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl, (C ₇ -C ₁₈ )aralkyl, (C=S)-SR ⁶ , wherein R ^{6 is} selected from the group consisting of (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C ₁₈ )Aralkyl; and -M ¹ (R ⁷ ) _c (R ⁸ ) _d , wherein M ¹ is ruthenium or tin, and each R ^{7 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C ₁₈ )aralkyl; each R ⁸ independently Selected from -SR ³ -Si(OR ¹ ) _r (R ² ) _s , wherein R ¹ , R ² and R ³ are as defined above for formula 3, r is independently selected from integers of 1, 2 and 3 and s Is an integer independently selected from 0, 1 and 2, wherein r + s = 3; c is an integer independently selected from 2 and 3; d is an integer independently selected from 0 and 1; and c + d = 3 ;

Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₆ )aryl and (C ₇ -C ₁₆ )aralkyl;

Wherein each of R ¹³ , R ¹⁴ , R ¹⁸ and R ^{19 is} independently selected from (C ₁ -C ₁₆ )alkyl; R ¹⁵ and R ^{20 are} independently selected from divalent (C ₁ -C ₁₆ )alkyl, divalent (C ₆ -C ₁₈ )aryl, divalent (C ₇ -C ₁₈ )Aralkyl and -R ²⁴ -OR ²⁵ -, wherein R ²⁴ and R ^{25 are} independently selected from divalent (C ₁ -C ₆ ) Alkyl; R ¹⁶ and R ^{17 are} independently selected from (C ₁ -C ₁₆ )alkyl and -SiR ²⁶ R ²⁷ R ²⁸ , wherein R ²⁶ , R ²⁷ and R ^{28 are} independently selected from (C ₁ -C ₁₆ ) An alkyl group, a (C ₆ -C ₁₈ ) aryl group and a (C ₇ -C ₁₈ ) aralkyl group; each of R ²¹ and R ^{22 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ And aryl and (C ₇ -C ₁₈ ) aralkyl; each R ^{23 is} independently selected from hydrogen and (C ₁ -C ₆ )alkyl; and f, g, h and i are independently selected from 0, 1 and An integer of 2; f+g=2; and h+i=2;

Wherein each of R ²⁹ and R ^{30 is} independently selected from the group consisting of (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl, (C ₇ -C ₁₈ )aralkyl, and vinyl; and j is selected from An integer from 1 to 200; and wherein the amount of the polymer of Formula 1 is from 15 mol% to 85 mol% based on the total of the polymer of Formula 1 and the polymer of Formula 2.

The polymer composition of the present invention may comprise one or more other components selected from the group consisting of (i) components added to the polymerization process for preparing the polymers of Formulas 1 and 2 or formed by the polymerization process. And (ii) components that remain after removal of the solvent from the polymerization process. This embodiment of the first aspect of the invention is also referred to herein as "second polymer composition." The components added to the polymerization process include, inter alia, softeners (extender oils), stabilizers and polymers which are not polymers of formula 1 or formula 2. The components which are formed as a result of the polymerization process and which remain after removal of the solvent from the polymerization process include, in particular, polymers which are not polymers of formula 1 or formula 2.

The polymer composition of the present invention (first and second polymer compositions) may also comprise one or more other components added after the polymerization process, including one or more fillers, one or more polymerizations other than Formula 1 or Formula 2 Other polymers and one or more crosslinkers (vulcanizing agents). This embodiment of the first aspect of the invention is also referred to herein as "the third polymer composition." The components added after the polymerization are usually added to the polymer composition after the solvent is removed from the polymerization process, and are usually added under mechanical mixing.

In a second aspect, the invention provides a method of preparing a first aspect of a polymer composition, the method comprising the steps of: i) reacting a polymerization initiator mixture with one or more selected from the group consisting of conjugated dienes and aromatics The polymerizable monomer of the group vinyl compound is reacted to obtain a living polymer chain, and the polymerization initiator mixture can be obtained by formulating the following compound of formula 9:

Wherein each R ^{31 is} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl, and (C ₇ -C ₁₈ )aralkyl; each R ³² , R ³³ and R ³⁴ Independently selected from the group consisting of hydrogen, (C ₁ -C ₁₈ )alkyl and (C ₁ -C ₁₈ )alkoxy; k, l and q are independently selected from the integers of 0, 1, 2 and 3, and 10 compound reaction to obtain M ² -R ⁴¹ formula 10

Wherein M ² is selected from lithium, sodium, and potassium, and R ⁴¹ is selected from (C ₁ -C ₁₀₀₎ alkyl and (C ₂ -C ₁₀₀₎ alkenyl group, wherein each R ⁴¹ is optionally substituted with one to three (C ₆ - C ₁₂ ) aryl substituted and optionally bonded to M ² via an oligomer chain composed of up to 25 monomer units selected from the group consisting of conjugated dienes and aromatic vinyl compounds, especially such conjugated dienes 1,3-butadiene and isoprene, the aromatic vinyl compounds being especially styrene and divinylbenzene; wherein the living polymer chains contain at least 40% by weight of the conjugated diene a repeating unit obtained by polymerization, wherein the molar ratio of the compound of the formula 10 to the compound of the formula 9 is in the range of 1:1 to 8:1, and ii) the living polymer chain of the step i) is one or more selected from the group consisting of Chain end modifier reaction of compounds of formula 11 to formula 15:

Wherein R ¹ , R ² , R ³ , Z, r and s are as defined above for formula 3;

Wherein R ^9, R ^10, R ¹¹ and R ¹² are as defined above with respect to Formula 4;

Wherein R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are as defined above for formula 6; t is an integer selected from 1, 2 and 3; u is an integer selected from 0, 1 and 2; u=3;

Wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are as defined above for formula 7; v is an integer selected from 1, 2 and 3; w is an integer selected from 0, 1 and 2; And v+w=3;

Wherein each of R ²⁹ and R ^{30 is} as defined above for Formula 8; and x is an integer selected from 1 to 6; and wherein the chain end modifiers of Formula 11 to Formula 15 are used in the following amounts: (i) Formula 10 The molar ratio of the compound to the compound of formula 9 in the range of from 1:1 to 2.1:1, from 0.15 to 0.85 moles per mole of the compound of formula 10, and (ii) when the molar ratio of the compound of formula 10 to the compound of formula 9 is When it is greater than the range of 2.1:1 to 8:1, 0.5 to 3 moles per mole of the compound of the formula 10.

In a third aspect, the present invention provides a crosslinked polymer composition obtained by crosslinking a polymer composition of the present invention comprising one or more crosslinking (vulcanizing) agents.

In a fourth aspect, the invention provides a method of preparing a third aspect of a crosslinked polymer composition, the method comprising the step of crosslinking a polymer composition comprising one or more crosslinkers.

In a fifth aspect, the invention provides an article comprising at least one component formed from the crosslinked polymer composition of the invention. The article can be, for example, a tire, a tire tread, a tire sidewall, an automotive part, a footwear component, a golf ball, a belt, a gasket, a seal, or a hose.

Figure 1: Sliding friction coefficient of a polymer example.

Polymerization initiator mixture and preparation method

The polymerization initiator used to prepare the polymer composition of the first aspect of the present invention is the reaction product of the compound of the formula 9 with the compound of the formula 10. The reaction product is a compound 9a dianion of formula as defined above, having at least two are each connected to the metal atom M ² of the female carbon ions. Typical structures and methods of preparation of such products are described in, for example, EP 0 316 857, US 4,172, 190, US 5, 521, 255, US 5, 561, 210, and EP 0 413 294.

In one embodiment of the potential reaction between a compound of Formula 9a and a compound of Formula 9 and a compound of Formula 10, M ² is lithium; R ^{41 is} selected from (C ₁ -C ₁₀ )alkyl; each R ^{31 is} independently selected from And hydrogen (C ₁ -C ₁₀ )alkyl, preferably hydrogen; R ³² and R ³⁴ are the same and are selected from hydrogen and (C ₁ -C ₁₈ )alkyl; each R ^{33 is} independently selected from hydrogen and ( C ₁ -C ₁₈ )alkyl; all other substituents or groups are as defined generally with respect to formula 9 and formula 10.

Specific preferred classes of compounds of formula 9 include the following compounds:

Specific preferred classes of the compound of formula 10 include the following compounds: methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, phenyl lithium, hexyl lithium, preferably It is n-butyl lithium and second butyl lithium.

Specific preferred classes of compounds of formula 9a include those which can be obtained by reacting one or more of the above specific preferred classes of the compound of formula 9 with one or more of the above specific preferred classes of the compound of formula 10.

The molar ratio in the reaction between the compound of formula 10 and the compound of formula 9 is in the range of from 1:1 to 8:1, preferably from 1.5:1 to 8:1 and more preferably from 2:1 to 6:1. At ratios below 1:1, the amount of the compound of formula 9 remaining after reaction with the compound of formula 10 can cause significant gelation during the polymerization process. At a ratio greater than 8:1, the amount of the compound of formula 10 remaining after reaction with the compound of formula 9 will result in less than 15% of the polymer of formula 1 (based on the total amount of the polymer of formula 1 and the polymer of formula 2) .

In one embodiment, from 1 to 2.1 equivalents of a compound of formula 10 is reacted with one equivalent of a compound of formula 9. In this case (explaining experimental error), the entire amount of the compound of formula 10 is reacted with the compound of formula 9. In the subsequent preparation of the polymer composition of the present invention, it is then necessary to use a chain end modifier of the formula 11 to formula 15 in an amount of a molar amount (molar equivalent) relative to the molar amount of the compound of the formula 9 so as to A composition comprising the polymer of Formula 1 and Formula 2 is obtained.

In an alternate embodiment, more than 2.1 and up to 8 equivalents of a compound of formula 10 It is reacted with 1 equivalent of the compound of the formula 9 to thereby obtain a mixture (composition) of the dianion initiator (formula 9a) and the monoanion initiator (the remaining compound of the formula 10). In this case, the molar amount of the chain end modifier of the formula 11 to the formula 15 to be used in the preparation of the polymer composition of the present invention may be less than, equal to or greater than the molar amount of the compound of the formula 9 (corresponding to the formula The molar amount of the 9a compound). The preferred molar ratio of the compound of formula 10 to the compound of formula 9 in this embodiment is greater than 2.1:1 to 7:1, more preferably greater than 2.1:1 to 6:1, even more preferably 2.5:1 to 3.5:1. Within the range or roughly 3:1.

The process for preparing the polymerization initiator mixture comprises the step of reacting a starter precursor compound of formula 9 with at least one compound of formula 10, optionally in the presence of a Lewis base. The reaction is preferably carried out in a non-polar solvent, including a hydrocarbon solvent, including aliphatic and aromatic solvents, preferably aliphatic solvents such as hexane, heptane, pentane, synthetic isoparaffin, cyclohexane and Executed in the cyclohexane, and usually carried out at a temperature ranging from -60 ° C to 130 ° C, preferably from 0 ° C to 100 ° C and even more preferably from 20 ° C to 70 ° C for 2 seconds to 10 days. Preferably, the period is from 5 seconds to 5 days, and even more preferably from 10 seconds to 2 days.

In one embodiment, the compound of formula 10 can be reacted with up to 25 monomeric molecules selected from the group consisting of conjugated dienes and aromatic vinyl compounds prior to reaction with the compound of formula 9, especially conjugated dienes. Butadiene and isoprene, these aromatic vinyl compounds are especially styrene. The resulting "oligomer" in the scope of Formula 10 is then reacted with an initiator precursor compound of Formula 9 as described herein.

Optionally, the Lewis base can be added to the pre-formula precursor compound prior to the addition of the compound of formula 10 and reacting with the compound of formula 10 to be present in the reaction at the outset. Alternatively, it can be added during the reaction or after the reaction is completed. Any such alternative addition will result in the formation of a Lewis base adduct from the reaction product, i.e., from the compound of formula 9a. When a Lewis base is present, it is usually in a ratio of from 0.01 to 20, preferably from 0.05 to 5.0 and even more preferably from 0.1 to 3.0, based on the molar equivalent of the starting agent precursor compound of the formula 9 to the Lewis base. use.

With regard to increasing the storage stability (shelf life) of the polymerization initiator mixture, it is possible to obtain the resulting reaction mixture containing the polymerization initiator mixture and including the alkali metal M ² and one or more selected from the group consisting of conjugated diene monomers and aromatic The polymerizable monomers of the group vinyl compound are contacted, and the conjugated diene monomers are especially selected from the group consisting of butadiene and isoprene, and the aromatic vinyl compounds are especially styrene. For this purpose, it is suitable to use a polymerizable monomer in an amount of up to 1000 equivalents, preferably up to 200 equivalents, and most preferably up to 75 equivalents per alkali metal equivalent.

Polymer composition

The first aspect of the polymer composition of the present invention comprises a modified elastomeric polymer according to Formulas 1 and 2 as defined herein. In general, the amount of the polymer of Formula 1 is from 15 to 85 mole % based on the total of the polymer of Formula 1 and the polymer of Formula 2. If the amount of the polymer of Formula 1 is greater than 85 mol%, the processability of the polymer composition can be adversely affected when additionally containing one or more fillers. If the amount of the polymer of Formula 1 is less than 15 mol%, the effectiveness of the crosslinked polymer composition of the present invention can be adversely affected, especially in terms of rolling resistance.

Specific preferred embodiments of the polymer of Formula 1 include, but are not limited to, the following structure (wherein P ^{1 is} as defined herein): [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OEt)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OPr)(Me)] ₂ P ¹ , [ Me ₃ Si-S-(CH ₂ ) ₃ -Si(OBu)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OMe)(Me)] ₂ P ¹ , [Et ₃ Si- S-(CH ₂ ) ₃ -Si(OEt)(Me)] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [Et ₃ Si-S- (CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OPr)(Me)] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OBu)(Me)] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [Et ₃ Si-S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S- (CH ₂ ) ₃ -Si(OEt)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si- S-(CH ₂ ) ₃ -Si(OPr)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OBu)(Me)] ₂ P ¹ , [( Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-S -(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-Si(OEt)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₂ -Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₂ -Si(OEt)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )- C(H)Me-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) -C(H)Me-(CH ₂ )-Si(OEt)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [ (Bu)Me ₂ Si-S-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-Si(OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-Si(OEt)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OEt )(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ ,[(Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-C(H) Me-(CH ₂ )-Si(OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OEt)( Me)] ₂ P ¹ , [Me ₃ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-SC(H)Me -(CH ₂ ) ₂ -Si(OEt)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [ (Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ ,[(Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si (OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OEt)(Me)] ₂ P ¹ , [Me ₃ Si-S- (CH ₂ ) ₁₁ -Si(OMe) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OEt) ₂ ] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OMe)(Me)] ₂ P ¹ , [Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OEt)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S-( CH ₂ ) ₁₁ -Si(OMe) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH _{2 11} -Si(OEt) ₂ ] ₂ P ¹ , [(Bu)Me ₂ Si-S-(CH ₂ ) ₁₁ -Si(OMe)(Me)] ₂ P ¹ , [(Bu)Me ₂ Si-S -(CH ₂ ) ₁₁ -Si(OEt)(Me)] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si( OMe) ₂ ] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(MeO ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S -Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-( CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(BuO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si (OBu) ₂ ] ₂ P ¹ , [(BuO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [( BuO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH _{2 ) 3} -Si(Me)(OMe)] ₂ P ¹ ,[(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me (OMe)] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe)(Me)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)] ₂ P ¹ , [(Me (EtO) ₂ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si -(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt)(Me)] ₂ P ¹ , [(MeO) ₂ (Me)Si-CH ₂ -C( H) Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)] ₂ P ¹ , [(MeO) ₂ (Me)Si -CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)] ₂ P ¹ ,[(EtO ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt)(Me)] ₂ P ¹ , [(EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si (Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt )(Me)] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₂ Si-(CH ₂ )-S-Si(Et) ₂ -S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ )-S-Si(Me ₂ -S-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ )-S-Si(Et) ₂ -S-(CH ₂ )-Si(OEt ) ₂ ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si(Me)(OMe)] ₂ P ¹ , [(Me) (MeO) ₂ Si-(CH ₂ )-S-Si(Et) ₂ -S-(CH ₂ )-Si(Me)(OMe)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si(Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ )-S-Si(Et ₂ -S-(CH ₂ )-Si(Me)(OEt)] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si( Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₂ Si- (CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn (Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-(CH _{2 3} -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ - S-(CH ₂ ) ₃ -Si(OPr) ₂ ] ₂ P ¹ , [(BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OBu ₂ ] ₂ P ¹ , [(BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [(BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OMe)] ₂ P ¹ ,[(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Et ₂ -S-(CH ₂ ) ₃ -Si(Me)(OMe)] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-( CH ₂ ) ₃ -Si(OMe)(Me)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si (Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH _{2 3} -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Sn (Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt)(Me)] ₂ P ¹ ,[(MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn (Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)] ₂ P ¹ , [(MeO) ₂ (Me)Si-CH ₂ -C(H)Me- CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)] ₂ P ¹ , [(EtO) ₂ (Me)Si-CH ₂ - C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt)(Me)] ₂ P ¹ ,[(EtO) ₂ (Me Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) (Me)] ₂ P ¹ , (MeO) ₃ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ )-S- Sn(Et) ₂ -S-(CH ₂ )-Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )- Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ )-Si(OEt) ₂ ] ₂ P ¹ , [(Me (MeO) ₂ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )-Si(Me)(OMe)] ₂ P ¹ , [(Me)(MeO) ₂ Si-( CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ )-Si(Me)(OMe)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ )-S-Sn( Me) ₂ -S-(CH ₂ )-Si(Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ )-Si(Me)(OEt) ] ₂ P ¹ , [(MeO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [(MeO) ₃ Si -(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₂ -S-Sn( Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [(EtO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe) ] ₂ P ¹ , [(Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)] ₂ P ¹ , [ (Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)] ₂ P ¹ , [(Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)] ₂ P ¹ ,

Specific preferred embodiments of the polymer of Formula 2 include, but are not limited to, the following structure (wherein P ^{2 is} as defined herein): Me ₃ Si-S-(CH ₂ ) ₃ -Si(OMe)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OEt)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OPr)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OBu) (Me)P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , Et ₃ Si- S-(CH ₂ ) ₃ -Si(OMe)(Me)P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OEt)(Me)P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OPr)(Me)P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OBu)(Me)P ² , Et ₃ Si-S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , Et ₃ Si-S- (CH ₂ ) ₃ -Si(OBu) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OMe)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OEt)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OPr)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ - Si(OBu)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si (OPr) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , Me ₃ Si-S-(CH ₂ )-Si(OMe) ₂ P ² , Me ₃ Si-S-(CH ₂ )-Si(OEt) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₂ - Si(OEt) ₂ P ² , Me ₃ Si-S-(CH ₂ )-Si(OMe)(Me)P ² , Me ₃ Si-S-(CH ₂ )-Si(OEt)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₂ -Si(OMe)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₂ -Si(OEt)(Me)P ² ,Me ₃ Si-S -(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe) ₂ P ² ,Me ₃ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OEt ₂ P ² , Me ₃ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe)(Me)P ² , Me ₃ Si-S-(CH ₂ )-C( H) Me-(CH ₂ )-Si(OEt)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ )-Si(OMe) ₂ P ² , (Bu)Me ₂ Si-S- (CH ₂ )-Si(OEt) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OEt) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ )-Si(OMe)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ )-Si(OEt (Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OMe)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₂ -Si(OEt (Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe) ₂ P ² , (Bu)Me ₂ Si-S-( CH ₂ )-C(H)Me-(CH ₂ )-Si(OEt) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OMe)(Me)P ² ,(Bu)Me ₂ Si-S-(CH ₂ )-C(H)Me- (CH ₂ )-Si(OEt)(Me)P ² , Me ₃ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , Me ₃ Si-SC(H)Me-( CH ₂ ) ₂ -Si(OEt) ₂ P ² , Me ₃ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe)(Me)P ² , Me ₃ Si-SC(H)Me-( CH ₂ ) ₂ -Si(OEt)(Me)P ² , (Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe) ₂ P ² ,(Bu)Me ₂ Si-SC (H)Me-(CH ₂ ) ₂ -Si(OEt) ₂ P ² , (Bu)Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OMe)(Me)P ² ,(Bu Me ₂ Si-SC(H)Me-(CH ₂ ) ₂ -Si(OEt)(Me)P ² , Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OMe) ₂ P ² ,Me ₃ Si -S-(CH ₂ ) ₁₁ -Si(OEt) ₂ P ² , Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OMe)(Me)P ² ,Me ₃ Si-S-(CH ₂ ) ₁₁ -Si(OEt)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₁₁ -Si(OMe) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₁₁ -Si (OEt) ₂ P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₁₁ -Si(OMe)(Me)P ² , (Bu)Me ₂ Si-S-(CH ₂ ) ₁₁ -Si(OEt (Me)P ² , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (MeO) ₃ Si-( CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S -(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (E tO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Si (Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si (OEt) ₂ P ² , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , (PrO) ₃ Si-( CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² ,(PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S -(CH ₂ ) ₃ -Si(OPr) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S -Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OMe)P ² ,(Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me)( OMe)P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe)(Me)P ² , (Me)( EtO) ₂ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me) (OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt)(Me)P ² ,(MeO) ₂ (Me Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)P ² ,(MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe)(Me)P ² , (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt)(Me) P ² , (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) (Me)P ² , (MeO) ₃ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) -S-Si(Et) ₂ -S-(CH ₂ )-Si(OMe) ₂ P ² , (EtO) ₃ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )- Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ )-S-Si(Et) ₂ -S-(CH ₂ )-Si(OEt) ₂ P ² , (Me)(MeO) ₂ Si -(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si(Me)(OMe)P ² ,(Me)(MeO) ₂ Si-(CH ₂ )-S-Si(Et ₂ -S-(CH ₂ )-Si(Me)(OMe)P ² ,(Me)(EtO) ₂ Si-(CH ₂ )-S-Si(Me) ₂ -S-(CH ₂ )-Si (Me)(OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ )-S-Si(Et) ₂ -S-(CH ₂ )-Si(Me)(OEt)P ² ,(MeO ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Si( Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si( OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ P ² , (Me)(MeO) ₂ Si-(CH _{2 2} -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)P ² ,(Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)P ² ,(Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)P ² , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) ₃ - S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ P ² ,(PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OBu) ₂ P ² , (BuO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S- (CH ₂ ) ₃ -Si(OBu) ₂ P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)( OMe)P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OMe)P ² ,(Me)( MeO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe)(Me)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)P ² ,(Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(Me)(OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ - Si(OEt)(Me)P ² , (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C(H)Me- CH ₂ - Si(OMe)(Me)P ² , (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H Me-CH ₂ -Si(OMe)(Me)P ² ,(EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ - C(H)Me-CH ₂ -Si(OEt)(Me)P ² ,(EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S- CH ₂ -C(H)Me-CH ₂ -Si(OEt)(Me)P ² ,(MeO) ₃ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )-Si( OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ )-Si(OMe) ₂ P ² , (EtO) ₃ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )-Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ ) -Si(OEt) ₂ P ² , (Me)(MeO) ₂ Si-(CH ₂ )-S-Sn(Me) ₂ -S-(CH ₂ )-Si(Me)(OMe)P ² , (Me (MeO) ₂ Si-(CH ₂ )-S-Sn(Et) ₂ -S-(CH ₂ )-Si(Me)(OMe)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) -S-Sn(Me) ₂ -S-(CH ₂ )-Si(Me)(OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ )-S-Sn(Et) ₂ -S- (CH ₂ )-Si(Me)(OEt)P ² ,(MeO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₂ -S -Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ P ² , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)P ² , (Me)(MeO) ₂ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OMe)P ² ,(Me)(EtO) ₂ Si- (CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)P ² , (Me)(EtO) ₂ Si-(CH ₂ ) ₂ -S-Sn (Et) ₂ -S-(CH ₂ ) ₂ -Si(Me)(OEt)P ² ,

A portion derived from a chain end modification method using a chain end modifier and having a terminal trihydrocarbyl decyl group (including a trialkyl decyl group, a dialkyl aryl decyl group, and a triaryl decyl group) serves as a polymer chain preventing group. A protecting group that is not intended for subsequent reaction. The protecting groups can be removed by exposure to a compound containing a reactive hydroxyl group (-OH) such as water, an alcohol, and an organic or inorganic acid such as hydrochloric acid, sulfuric acid or a carboxylic acid. These exposure conditions are typically present during vulcanization. In the case where the terminal group of the chain-end modifier is attached to the sulfide, exposure to the reactive hydroxyl group and removal of the protecting group will result in the formation of an unprotected thiol group (SH) as an end group of the polymer chain. Depending on the processing conditions of the modified polymer (e.g., stripping), both the unprotected modified polymer and the protected modified polymer may be present.

It is believed that a particular end group of the polymer, such as an unprotected thiol group, is reactive with a filler such as cerium oxide and/or carbon black, which can result in a more uniform distribution of the filler within the polymer composition.

Specific preferred examples of polymers containing unprotected terminal thiol groups include the following polymers, including their Lewis base adducts (wherein P ¹ and P ^{2 are} as defined herein): [HS-(CH ₂ ) ₃ - Si(OH)(Me)] ₂ P ¹ , [HS-(CH ₂ ) ₃ -Si(OH) ₂ ] ₂ P ¹ , [HS-(CH ₂ ) ₃ -Si(OH)(Et)] ₂ P ¹ , [HS-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OH) ₂ ] ₂ P ¹ , [HS-(CH ₂ )-C(H)Me-(CH ₂ )- Si(OH)(Me)] ₂ P ¹ , [HS-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OH)(Et)] ₂ P ¹ , [HS-(CH ₂ ) -Si(OH) ₂ ] ₂ P ¹ , [HS-(CH ₂ )-Si(OH)(Me)] ₂ P ¹ , [HS-(CH ₂ )-Si(OH)(Et)] ₂ P ¹ , [HS-(CH ₂ ) ₂ -Si(OH) ₂ ] ₂ P ¹ , [HS-(CH ₂ ) ₂ -Si(OH)(Me)] ₂ P ¹ , [HS-(CH ₂ ) ₂ - Si(OH)(Et)] ₂ P ¹ , [HS-(CH ₂ )-C(Me) ₂ -(CH ₂ )-Si(OH) ₂ ] ₂ P ¹ , [HS-(CH ₂ )-C (Me) ₂ -(CH ₂ )-Si(OH)(Me)] ₂ P ¹ , [HS-(CH ₂ )-C(Me) ₂ -(CH ₂ )-Si(OH)(Et)] ₂ P ¹ , [HS-C(H)Me-(CH ₂ ) ₂ -Si(OH) ₂ ] ₂ P ¹ , [HS-C(H)Me-(CH ₂ ) ₂ -Si(Me)(OH) ] ₂ P ¹ , [HS-C(H)Me-(CH ₂ ) ₂ -Si(Et)(OH)] ₂ P ¹ , HS-(CH ₂ ) ₃ -Si(OH)(Me)P ² , HS-(CH ₂ ) ₃ -Si(OH) ₂ P ² , HS-(CH ₂ ) ₃ -Si(OH)(Et)P ² , HS-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OH) ₂ P ² , HS-(CH ₂ )-C(H)Me-(CH ₂ )-Si(OH)(Me)P ² , HS-(CH ₂ )-C(H) Me-(CH ₂ )-Si(OH)(Et)P ² , HS-(CH ₂ )-Si(OH) ₂ P ² , HS-(CH ₂ )-Si(OH)(Me)P ² , HS -(CH ₂ )-Si(OH)(Et)P ² , HS-(CH ₂ ) ₂ -Si(OH) ₂ P ² , HS-(CH ₂ ) ₂ -Si(OH)(Me)P ² , HS-(CH ₂ ) ₂ -Si(OH)(Et)P ² , HS-(CH ₂ )-C(Me) ₂ -(CH ₂ )-Si(OH) ₂ P ² , HS-(CH ₂ ) -C(Me) ₂ -(CH ₂ )-Si(OH)(Me)P ² , HS-(CH ₂ )-C(Me) ₂ -(CH ₂ )-Si(OH)(Et)P ² , HS-C(H)Me-(CH ₂ ) ₂ -Si(OH) ₂ P ² , HS-C(H)Me-(CH ₂ ) ₂ -Si(Me)(OH)P ² , HS-C( H) Me-(CH ₂ ) ₂ -Si(Et)(OH)P ² .

The reaction product of the chain-end modified polymer typically contains a stanol group and an alkoxyalkyl group, and the total amount thereof is from 0.01 to 3,000 mmol/kg of the polymer, preferably from 0.05 to 1,500 mmol/kg, more preferably from 0.1 to 500 mmol/kg and even more preferably 0.2 to 200 mmol/kg.

The reaction product of the chain-end modified polymer preferably contains a sulfide group (in the form of a protecting group attached to a thiol group and/or a sulfide group) in a total amount of 0.01 to 1000 mmol/kg of a polymer, preferably From 0.05 to 500 mmol/kg, more preferably from 0.1 to 300 mmol/kg and even more preferably from 0.2 to 200 mmol/kg of polymer.

For most applications, the polymers P ¹ and P ^{2 are} preferably homopolymers derived from conjugated dienes, copolymers derived from conjugated diene monomers and aromatic vinyl monomers, and/or one or A terpolymer of two types of conjugated dienes with one or two types of aromatic vinyl compounds. Examples of particularly suitable polymers include homopolymers of butadiene or isoprene and random or block copolymers and terpolymers of butadiene, isoprene and styrene, especially butadiene. Random copolymer with isoprene and random or block copolymer of butadiene and styrene.

In the polymers P ¹ and P ² , the aromatic vinyl monomer constitutes up to 60% by weight, preferably 2% by weight to 55% by weight and more preferably 5% by weight to 50% by weight based on the total weight of the polymer weight%. An amount of less than 2% by weight may result in a balance of deterioration in rolling resistance, slip and abrasion resistance and result in reduced tensile strength, while an amount greater than 60% by weight may result in increased hysteresis loss. The polymer may be a block or random copolymer of an aromatic vinyl monomer, and is preferably bonded to 40% by weight or more by weight to 40% by weight of the aromatic vinyl monomer unit, and 10% by weight or less. 10% by weight is the polymer "block" of eight or more than eight aromatic vinyl monomers connected in succession (the length of the successively attached aromatic vinyl units can be obtained by Tanaka et al. (Polymer, Vol. 22, The ozonolysis-gel permeation chromatography method developed by pp. 1721-1723 (1981). Copolymers outside this range tend to exhibit increased hysteresis loss.

Although there is no particular limitation on the content of the 1,2-bond and/or 3,4-bond of the conjugated diene moiety of the polymers P ¹ and P ² (hereinafter referred to as "vinyl bond content"), For most applications, the vinyl bond content is preferably from 2% to 90% by weight, particularly preferably from 4% to 80% by weight, based on the total weight of the diene portion. If the vinyl bond content in the polymer is less than 2% by weight, the resulting product may have a poor balance of wet skid resistance, rolling resistance and abrasion resistance. If the vinyl content in the polymer exceeds 90% by weight, the resulting product may exhibit deteriorated tensile strength and wear resistance as well as relatively large hysteresis loss.

monomer

The monomers used to prepare the polymers of the present invention are selected from the group consisting of conjugated olefins and, optionally, from aromatic vinyl compounds.

Suitable conjugated olefins include conjugated dienes such as 1,3-butadiene, 2-alkyl-1,3-butadiene, isoprene (2-methyl-1,3-butadiene) ), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, and 1,3-cyclooctadiene, and both or more The combination. 1,3-butadiene and isoprene are preferred conjugated olefins, and 1,3-butadiene is a particularly preferred conjugated olefin.

Suitable aromatic vinyl compounds include styrene, C _1-4 alkyl substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethyl Styrene, 2,4,6-trimethylstyrene, α-methylstyrene and stilbene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, vinyl benzate Dimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene and vinylpyridine and two thereof Or more than a combination of the two. Styrene is a particularly preferred aromatic vinyl compound.

In addition to the conjugated olefins and aromatic vinyl compounds mentioned above, it is also possible to use one or more monomers selected from the group consisting of olefins and non-conjugated dienes, such as C _{2 -} C ₂₀ α- Olefins and non-conjugated C _4- C ₂₀ diolefins, especially norbornadiene, ethylidene norbornene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 4-vinylcyclohexene and divinylbenzene (including 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene) and mixtures thereof.

In one embodiment, the amount of divinylbenzene (including 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene) is 1 mol% or less. Molar % (based on the total molar amount of the monomer used to prepare the polymer).

Chain end modifier

According to a second aspect of the invention, one or more chain end modifiers (or in short "modifiers") are used to react with the ends of the polymer chains obtained from the process of the second invention. In general, decane-sulfide ω chain end modifiers such as disclosed in WO 2007/047943, WO 2009/148932, US 6,229, 036, and US 2013/0131263 may be used for this purpose, each of which is incorporated by reference in its entirety. This article.

In a preferred embodiment, the chain end modifying agent is selected from one or more of the chain end modifying agents represented by Formulas 11 to 15. In a particularly preferred embodiment, the chain end modifier is selected from one or more compounds represented by Formula 11. A particularly preferred class of chain end modifiers of formula 11 includes the following compounds: (MeO) ₃ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (PrO) ₃ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (BuO) ₃ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (EtO) ₃ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (BuO) ₃ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (MeO) ₃ Si-CH ₂ -S-SiMe ₃ , (EtO) ₃ Si-CH ₂ -S-SiMe ₃ , (PrO) ₃ Si-CH ₂ -S-SiMe ₃ , (BuO) ₃ Si- CH ₂ -S-SiMe ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (PrO ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (BuO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , ((MeO) ₃ Si-CH ₂ -C( H) Me-CH ₂ -S-SiMe ₃ , (EtO) ₃ Si-CH ₂ -C(H)Me-CH ₂ - S-SiMe ₃ , (PrO) ₃ Si-CH ₂ -C(H)Me- CH ₂ -S-SiMe ₃ , (BuO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiMe ₃ (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiMe ₃ , (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiMe ₃ , (BuO) ₂ (Me)Si- (CH ₂ ) ₃ -S-SiMe ₃ , (MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiMe ₃ , (EtO) ₂ (Me)Si-( CH ₂ ) ₂ -S-SiMe ₃ , (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiMe ₃ , (BuO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiMe ₃ , (MeO) ₂ (Me)Si-CH ₂ -S-SiMe ₃ , (EtO) ₂ (Me)Si-CH ₂ -S-SiMe ₃ , (PrO) ₂ (Me)Si-CH ₂ -S-SiMe ₃ (BuO) ₂ (Me)Si-CH ₂ -S-SiMe ₃ , (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (EtO) ₂ (Me)Si- CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (PrO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (BuO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , ((MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (EtO) ₂ (Me)Si-CH ₂ -C (H)Me-CH ₂ -S-SiMe ₃ , (PrO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (BuO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (MeO)(Me) ₂ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (EtO)(Me) ₂ Si-(CH ₂ ) ₃ - S-SiMe ₃ , (PrO)Me) ₂ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (BuO)(Me) ₂ Si-(CH ₂ ) ₃ -S-SiMe ₃ , (MeO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (EtO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (PrO)(Me) ₂ Si-(CH ₂ ) ₂ -S -SiMe ₃ , (BuO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiMe ₃ , (MeO)(Me) ₂ Si-CH ₂ -S-SiMe ₃ , (EtO)(Me) ₂ Si- _{CH 2 -S-SiMe 3, (} PrO) (Me) 2 Si-CH 2 -S-SiMe 3 _{(BuO) (Me) 2 Si} -CH 2 -S-SiMe 3, (MeO) (Me) 2 Si-CH 2 -CMe 2 -CH 2 -S-SiMe 3, (EtO) (Me) 2 Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (PrO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , (BuO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiMe ₃ , ((MeO)(Me) ₂ Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (EtO)(Me) ₂ Si-CH ₂ -C( H) Me-CH ₂ -S-SiMe ₃ , (PrO)(Me) ₂ Si-CH ₂ -C(H)Me-CH ₂ -S-SiMe ₃ , (BuO)(Me) ₂ Si-CH ₂ - C(H)Me-CH ₂ -S-SiMe ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (PrO ₃ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (BuO) ₃ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-SiEt ₃ , ( EtO) ₃ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (BuO) ₃ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (MeO) ₃ Si-CH ₂ -S-SiEt ₃ , (EtO) ₃ Si-CH ₂ -S-SiEt ₃ , (PrO) ₃ Si-CH ₂ -S-SiEt ₃ , (BuO) ₃ Si-CH ₂ -S-SiEt ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (BuO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , ((MeO) ₃ Si-CH ₂ -C(H) Me-CH ₂ -S-SiEt _{3 (EtO) 3 Si-CH 2} -C (H) Me-CH 2 -S-SiEt 3, (PrO) 3 Si-CH 2 -C (H) Me-CH 2 -S-SiEt 3, (BuO) 3 Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiEt ₃ , (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiEt ₃ , (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-SiEt ₃ , (BuO) ₂ (Me)Si-(C H ₂ ) ₃ -S-SiEt ₃ , ( MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiEt ₃ , (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiEt ₃ , (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiEt ₃ , (BuO) ₂ (Me)Si-(CH ₂ ) ₂ -S-SiEt ₃ , (MeO) ₂ (Me)Si-CH ₂ -S-SiEt ₃ , (EtO) ₂ (Me)Si-CH ₂ -S-SiEt ₃ , (PrO) ₂ (Me)Si-CH ₂ -S-SiEt ₃ , (BuO) ₂ (Me)Si-CH ₂ -S-SiEt ₃ , (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (PrO) ₂ (Me) Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (BuO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , ((MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (PrO) ₂ (Me)Si -CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (BuO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (MeO)(Me) ₂ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (EtO)(Me) ₂ Si-(CH ₂ ) ₃ -S- SiEt ₃ , (PrO)Me) ₂ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (BuO)(Me) ₂ Si-(CH ₂ ) ₃ -S-SiEt ₃ , (MeO)(Me) ₂ Si -(CH ₂ ) ₂ -S-SiEt ₃ , (EtO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (PrO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (BuO)(Me) ₂ Si-(CH ₂ ) ₂ -S-SiEt ₃ , (MeO)(Me) ₂ Si-CH ₂ -S-SiEt ₃ , (EtO)(Me) ₂ Si-CH ₂ -S-SiEt ₃ , (PrO)(Me) ₂ Si-CH ₂ -S-SiEt ₃ , (BuO)(Me) ₂ Si-CH ₂ -S-SiEt ₃ , (MeO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (EtO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (PrO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , (BuO)(Me) ₂ Si-CH ₂ -CMe ₂ -CH ₂ -S-SiEt ₃ , ((MeO)(Me) ₂ Si-CH ₂ -C(H)Me -CH ₂ -S-SiEt ₃ , (EtO)(Me) ₂ Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (PrO)(Me) ₂ Si-CH ₂ -C(H Me-CH ₂ -S-SiEt ₃ and (BuO)(Me) ₂ Si-CH ₂ -C(H)Me-CH ₂ -S-SiEt ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S -Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si (OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ - S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ - Si(OEt) ₃ , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr), (PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₃ , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₃ , (MeO) ₃ Si-(CH _{2 2} -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S-(CH _{2 2} -Si(OMe) ₃ , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₃ , (EtO) ₃ Si-( CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S-( CH ₂ ) ₂ -Si(OEt) ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₃ , (PrO) ₃ Si -(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S -(CH ₂ ) ₂ -Si(OPr) ₃ , (MeO) ₃ Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ - S-Si(Et) ₂ -S-CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -S-Si(B u) ₂ -S-CH ₂ -Si(OMe) ₃ , (EtO ) ₃ Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si-CH ₂ -S-Si(Bu ₂ -S-CH ₂ -Si(OEt) ₃ , (PrO) ₃ Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -Si(OPr) ₃ , (MeO ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ - CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₃ ,(EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ , (EtO ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ , (PrO) ₃ Si-CH ₂ -CMe ₂ - CH ₂ -S-Si(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₃ , (MeO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ - C(H)Me-CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H) Me-CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₃ , (EtO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt ₃ , (EtO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₃ ,( EtO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₃ ,(PrO) ₃ Si -CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ - C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ -C(H) Me-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ , (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S- Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ ( Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (EtO) ₂ (Me) Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₃ - S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Me) ₂ -S- (CH ₂ ) ₃ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Si(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ (Me), (MeO) ₂ ( Me)Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₂ - S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S- (CH ₂ ) ₂ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (EtO) ₂ ( Me)Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ - S-Si(Me) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Si(Et) ₂ -S- (CH ₂ ) ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Si(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -S-Si( Bu) ₂ -S-CH ₂ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OEt) ₂ (Me ), (EtO) ₂ (Me)Si-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -S- Si(Bu) ₂ -S-CH ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ - S-Si(Bu) ₂ -S-CH ₂ -Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Me) ₂ -S- CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₂ (Me ), (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₂ (Me), (PrO ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me )Si-CH ₂ -CMe ₂ -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Si (Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si( Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S- Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ - S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H)Me -CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H Me-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -C (H)Me-CH ₂ -S-Si(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Si(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si- CH ₂ -C(H)Me-CH ₂ -S-Si(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me), (MeO) ₃ Si-( CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-( CH ₂ ) ₃ - Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₃ , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr), (PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH _{2 3} -Si(OPr) ₃ , (PrO) ₃ Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₃ , (MeO) ₃ Si-( CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-( CH ₂ ) ₂ -Si(OMe) ₃ , (MeO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₃ , (EtO) ₃ Si -(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S -(CH ₂ ) ₂ -Si(OEt) ₃ , (EtO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₃ , (PrO) ₃ Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OPr) ₃ , ( MeO) ₃ Si-CH ₂ -S-Sn(Me) ₂ -S -CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -S-Sn (Bu) ₂ -S-CH ₂ -Si(OMe) ₃ , (EtO) ₃ Si-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si- CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -Si(OEt) ₃ , (PrO) ₃ Si-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ - Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -Si(OPr) ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S -Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₃ ,(MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₃ , (MeO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si( OMe) ₃ , (EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ , (EtO) ₃ Si- CH ₂ -CMe ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ ,(EtO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S -Sn(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₃ ,(PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₃ , (PrO) ₃ Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr ₃ , (MeO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₃ ,( MeO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₃ ,(MeO) ₃ Si -CH ₂ -C(H)Me-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₃ ,(EtO) ₃ Si-CH ₂ - C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₃ ,(EtO) ₃ Si-CH ₂ -C(H) Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₃ ,(EtO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₃ ,(PrO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn (Me) ₂ -SC H ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ - S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ ,(PrO) ₃ Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₃ , (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OMe ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S -(CH ₂ ) ₃ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Me) ₂ -S-(CH ₂ ) ₃ -Si(OPr ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Et) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₃ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₃ -Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S -(CH ₂ ) ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OMe ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Me) ₂ -S -(CH ₂ ) ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Et) ₂ -S-(CH ₂ ) ₂ -Si(OPr ₂ (Me), (PrO) ₂ (Me)Si-(CH ₂ ) ₂ -S-Sn(Bu) ₂ -S-(CH ₂ ) ₂ -Si(OP r) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si- CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ - Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me) Si-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ ( Me)Si-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -S-Sn(Bu) ₂ -S -CH ₂ -Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ - Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OMe) ₂ (Me) (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me) Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Bu) ₂ - S-CH ₂ -CMe ₂ -CH ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -CM e ₂ -CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -CMe ₂ -CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -CMe ₂ -CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -CMe ₂ -CH ₂ - Si(OPr) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me -CH ₂ -Si(OMe) ₂ (Me), (MeO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Bu) ₂ -S-CH ₂ -C(H Me-CH ₂ -Si(OMe) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ -S-CH ₂ -C (H)Me-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₂ (Me), (EtO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Bu) ₂ -S- CH ₂ -C(H)Me-CH ₂ -Si(OEt) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Me) ₂ - S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-Sn(Et) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me), (PrO) ₂ (Me)Si-CH ₂ -C(H)Me-CH ₂ -S-S n(Bu) ₂ -S-CH ₂ -C(H)Me-CH ₂ -Si(OPr) ₂ (Me).

If more than one chain end modifier is used for the purpose of chain end modification, the chain end modifiers may be added successively to the solution of the living anionic polymer, or they may be mixed together, and then the resulting mixture is added to the living anion. In the solution of the polymer.

The chain end modifiers may be added intermittently (or at regular or irregular time intervals) or continuously during the polymerization, but preferably at a polymerization conversion of more than 80% and more preferably at a conversion of more than 90%. Add to. Preferably, a plurality of polymer chain ends are not blocked prior to reaction with the chain end modifier; that is, the living polymer chain ends are present and are capable of reacting with the modifying agent. This chain end modification reaction can occur before, after or during the addition of any coupling agent. Preferably, the chain end modification reaction is completed after the addition of any coupling agent. See, for example, WO 2009/148932, which is incorporated herein by reference.

Chain end modification method

The polymer composition according to the first aspect of the present invention is a reaction product of a living polymer chain comprising an α- and ω, ω'-anion-polymer chain end and at least one chain-end modifier. The living polymer chain comprising the α- and ω,ω′-anion polymer chain ends is a reaction of a starter mixture comprising at least one monoanionic polymerization initiator and at least one dianionic polymerization initiator and a monomer product. The monoanionic starter forms a reactive monoanionic polymer chain end (α-anionid chain end) after reacting with the monomer, and the dianion initiator forms an active dianion after reacting with the monomer Chain end (ω, ω'-anion ion polymer chain end). Each anion carbon polymer chain end can be reacted with one equivalent of a chain end modifier to produce an alpha or omega, omega' modified polymer chain end. According to the present invention, the reaction of the monoanionic polymer chain end with the modifying agent produces the alpha modified polymer chain of Formula 2, and the reaction of the two dianionic polymer chain ends with the modifying agent produces a) ω, ω' of Formula 1 a modified polymer chain (when the modifier is used stoichiometrically relative to the anionic polymer chain end), or b) an alpha modified polymer chain of formula 2 and a ω,ω' modified polymer chain of formula 1 Mixture (when the modifier is used in substoichiometric relative to the anionic polymer chain ends).

The chain end modifying agent can be added directly to the polymer solution without dilution; however, it may be beneficial to add a modifying agent such as a dissolved form in an inert solvent such as cyclohexane. The amount of the chain end modifier to be added to the polymerization may vary depending on the monomer type, the coupling agent, the chain end modifier, the reaction conditions, and the desired polymer characteristics. In the present invention, the amount of chain end modifying agent is specifically adjusted based on the molar ratio of the compounds of formulas 9 and 10 as defined herein. The polymer chain end modification reaction can be carried out at a temperature ranging from 0 ° C to 150 ° C, preferably from 15 ° C to 120 ° C and even more preferably from 30 ° C to 100 ° C. There is no limit to the duration of the chain end modification reaction. However, with regard to economical polymerization methods, such as in the case of batch polymerization processes, the chain end modification reaction typically stops about 5 to 60 minutes after the addition of the modifier.

A method for preparing a modified polymer of the present invention comprises at least the following steps A to C:

Step A: A compound of formula 9 is reacted with a compound of formula 10 to obtain a starter mixture of monoanionic and dianionic initiators.

Step B: reacting the starter mixture with one or more polymerizable monomers in a polymerization solvent and optionally in the presence of a monomer capable of reacting with more than one growing polymer chain, such as divinylbenzene, such The polymerizable monomer is selected from the group consisting of conjugated olefins, preferably selected from the group consisting of butadiene and isoprene, and optionally selected from the group consisting of aromatic vinyl compounds, preferably selected from the group consisting of styrene and alpha-methyl styrene. Suitable polymerization solvents include non-polar aliphatic and non-polar aromatic solvents, preferably hexane, heptane, butane, pentane, synthetic isoparaffin oil, cyclohexane, toluene and benzene.

Step C: The reaction product of Step A is reacted with at least one chain end modifier selected from Formula 11 to Formula 15 (as described herein), preferably selected from Formula 11, to form a chain end modified polymer.

Randomizer

The polar coordination compound, also known as a randomizer, may optionally be added to the polymerization to adjust the microstructure of the conjugated diene moiety (including the content of the vinyl bond of the polybutadiene moiety), or to adjust the aromatic vinyl compound. The composition of the distribution, thus acting as a random component. Two or more than two kinds of randomizers may be used in combination. Exemplary randomizers are Lewis bases and include, but are not limited to, ether compounds such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether , propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, alkyl tetrahydrofuranyl ether (such as methyltetrahydrofuranyl ether, ethyl tetrahydrofuranyl ether, propyltetrahydrofuranyl ether, butyl tetrahydrofuranyl ether, hexyl tetrahydrofuranyl ether , octyltetrahydrofuranyl ether), tetrahydrofuran, 2,2-(bistetrahydrofuranmethyl)propane, bistetrahydrofuran methyl formal, methyl ether of tetrahydrofuran methanol, diethyl ether of tetrahydrofuran methanol, butyl ether of tetrahydrofuran methanol, α-methoxy Tetrahydrofuran, dimethoxybenzene and dimethoxyethane; and tertiary amine compounds such as triethylamine, pyridine, N,N,N',N'-tetramethylethylenediamine, dipiperidinyl Methyl ether of ethane, N,N-diethylethanolamine, diethyl ether of N,N-diethylethanolamine, and N,N-diethylethanolamine. Examples of preferred randomizer compounds are identified in WO 2009/148932, which is incorporated herein by reference in its entirety. The randomizer will typically be from 0.012:1 to 10:1, preferably from 0.1:1 to 8:1 and more preferably from 0.25:1 to about 6:1 of the randomizer compound and the starter compound. The molar ratio is added.

Coupler

The polymeric composition of the present invention can optionally be reacted with one or more coupling agents to form a branched chain polymer.

The coupling agent includes tin tetrachloride, tin tetrabromide, tin tetrafluoride, tin tetraiodide, antimony tetrachloride, antimony tetrabromide, antimony tetrafluoride, antimony tetraiodide, alkyl tin and alkyl anthracene. Trihalide or dialkyl tin and dialkyl sulfonium dihalide. A polymer coupled with a tin or bismuth tetrahalide has up to four arms, and a polymer coupled with an alkyl tin and an alkyl sulfonium trihalide has up to three arms, and a dialkyl tin and a dialkyl sulfonium dihalide. The coupled polymer has up to two arms. Hexahalodidioxane or hexafluorodioxane can also be used as a coupling agent to produce a polymer having up to six arms. Suitable tin and antimony halide coupling agents include: SnCl ₄ , (R ₁ ) ₃ SnCl, (R ₁ ) ₂ SnCl ₂ , R ₁ SnCl ₃ , SiCl ₄ , R ₁ SiCl ₃ , (R ₁ ) ₂ SiCl ₂ , (R ₁ ) ₃ SiCl, Cl ₃ Si—SiCl ₃ , Cl ₃ Si—O—SiCl ₃ , Cl ₃ Sn—SnCl ₃ and Cl ₃ Sn—O—SnCl ₃ , wherein R ₁ is a hydrocarbon group, preferably an alkyl group. . Examples of the tin and cerium alkoxide coupling agent further include: Sn(OMe) ₄ , Si(OMe) ₄ , Sn(OEt) _{4 ,} and Si(OEt) ₄ . The optimum coupling agents are: SnCl ₄ , SiCl ₄ , Sn(OMe) ₄ and Si(OMe) ₄ .

The coupling agents may be added intermittently (either at regular or irregular time intervals) or continuously during the polymerization, but are preferably added at a conversion of more than 80% and more preferably at a conversion of more than 90%. The coupling agent will typically be added only after a high degree of conversion has been achieved.

For example, in the case where an asymmetric coupling is required, the coupling agent can be continuously added during the polymerization. This continuous addition is usually carried out in a reaction zone which is distinguished from the one in which the overall polymerization takes place. The coupling agent can be added to a polymerization mixture which is suitably mixed for distribution and reaction in a hydrocarbon solution such as cyclohexane. Typically, 0.01 to 2.0 mol, preferably 0.02 to 1.5 mol, and more preferably 0.04 to 0.6 mol of the coupling agent is used per 4.0 mol of the living anionic polymer chain end.

Preferably, a plurality of polymer chain ends are uncapped prior to reaction with the coupling agent; that is, the living polymer chain ends are present and are capable of reacting with the coupling agent in a polymer chain coupling reaction. This coupling reaction occurs before, after or during the addition of any chain end modifier. This coupling reaction is preferably completed prior to the addition of the chain end modifier. In some embodiments, between 5% and 20% of the active polymer chain ends as determined by GPC have been reacted with the coupling agent prior to the addition of the chain end modifier. In other embodiments, between 20% and 35% of the living polymer chain ends have been reacted with the coupling agent prior to the addition of the chain end modifier. In another embodiment, between 35% and 50% of the active polymer chain ends have been reacted with the coupling agent prior to the addition of the chain end modifier.

Combinations of different coupling agents can also be used to couple polymer chains, such as Bu ₂ SnCl ₂ and SnCl ₄ ; Me ₂ SiCl ₂ and Si(OMe) ₄ ; Me ₂ SiCl ₂ and SiCl ₄ ; SnCl ₄ and Si(OMe) ₄ ; SnCl ₄ and SiCl ₄ . In particular, it is desirable to use a combination of tin and a bismuth coupler in a tire tread compound containing cerium oxide and carbon black. In this case, the molar ratio of tin to antimony compound will generally range from 20:80 to 95:5; more typically from 40:60 to 90:10 and preferably from 60:40 to 85:15. Most typically, a coupling agent is used in an amount of from about 0.001 to 4.5 mmol per 100 grams of polymer. It is generally preferred to use from about 0.05 to about 0.5 mmol of coupling agent per 100 grams of polymer to achieve the desired Mooney viscosity and to enable subsequent chain end functionalization of the remaining living polymer portion. Larger amounts tend to produce polymers containing terminal reactive groups or are insufficiently coupled and only enable insufficient chain end modification.

The polymer coupling reaction can be from 0 ° C to 150 ° C, preferably from 15 ° C to 120 ° C. And even more preferably in the temperature range of 40 ° C to 100 ° C. There is no limit to the duration of the coupling reaction. However, with regard to economical polymerization processes, such as in the case of batch polymerization processes, the coupling reaction typically stops about 5 to 60 minutes after the addition of the coupling agent.

In a preferred embodiment of the invention, divinylbenzene is used as a coupling agent. Divinylbenzene will typically be added with the monomer prior to initiating polymerization by the addition of an initiator.

Method of preparing a polymer composition

The process for preparing the polymer composition according to the second aspect of the invention comprises the steps of: i) polymerizing a starter mixture obtainable by reacting a compound of formula 9 as defined herein with a compound of formula 10; One or more polymerizable monomers selected from the group consisting of conjugated dienes and aromatic vinyl compounds are reacted to obtain living polymer chains, wherein the living polymer chains contain at least 40% by weight of polymerization by the conjugated dienes a repeating unit obtained, wherein the molar ratio of the compound of formula 10 to the compound of formula 9 is in the range of 1:1 to 8:1, and ii) the living polymer chain of step i) is reacted with formula 11 as defined herein One or more chain end modifying agents of formula 15 are preferably one or more chain end diluents of formula 11 and are reacted under conditions as defined herein.

In one embodiment, the method of preparing the polymer composition comprises the steps of first reacting a compound of formula 9 with more than 2.1 and up to 8 mol equivalents of a compound of formula 10 to form a mixture of monoanionic and dianionic materials and further The mixture is reacted with at least one type of polymerizable monomer selected from the group consisting of a conjugated olefin and an aromatic vinyl compound, thereby forming a mixture of an α-monoanionic living polymer chain and an ω,ω′-dianionic active polymer chain, and Further adding at least one chain-end modifier of Formula 11 to Formula 15, preferably Formula 11, and reacting thereby forming a polymer composition comprising a) modified at one chain end (α-modified) The polymer of formula 2 and b) are polymers of formula 1 modified at both ends of the linear polymer chain end (ω, ω 'modified).

In another embodiment, the method of preparing the modified polymer comprises the steps of first reacting a compound of formula 9 with from 1 to 2.1 mol equivalents of a compound of formula 10 to form a double yin An ionic substance and further reacting the dianionic substance with at least one type of polymerizable monomer selected from the group consisting of a conjugated olefin and an aromatic vinyl compound, thereby forming an ω, ω'-dianion active polymer chain, and further adding And reacting at least one chain end modifier of formula 11 to formula 15, preferably of formula 11, wherein the ratio of the sum of the chain end modifiers to the compound of formula 10 is from 0.15 to 0.85, thereby forming a polymer composition, the polymer The composition comprises a) a polymer of formula 2 modified at one chain end (alpha modification) and b) a polymer modified at both ends of the linear polymer chain end (ω, ω 'modified) and optionally c) Unmodified polymer.

The method for preparing the polymer composition is conventionally carried out in a solution polymerization form in a polymerization solvent, wherein the polymer formed is substantially soluble in the reaction mixture or in a suspension/slurry polymerization form, wherein the formed The polymer is substantially insoluble in the reaction medium. Suitable polymerization solvents include non-polar aliphatic and non-polar aromatic solvents, preferably hexane, heptane, butane, pentane, synthetic isoparaffin oil, cyclohexane, toluene and benzene. The solution polymerization is usually carried out at a lower pressure, preferably below 10 MPa, preferably at a temperature ranging from 0 to 120 °C. The polymerization is generally carried out under batch, continuous or semi-continuous polymerization conditions.

In general, information on the application of polymerization techniques, including polar coordination compounds and promoters, each increases the reactivity of the initiator, randomly arranges the aromatic vinyl compound, and randomly arranges the introduction of the polymer. , 2-polybutadiene or 1,2-polyisoprene or 3,4-polyisoprene units; amount of each compound; monomer; and suitable method conditions are described in WO 2009/148932 This document is fully incorporated herein by reference.

Polymer composition - other components

The polymer composition according to the first aspect of the present invention may additionally comprise one or more other components selected from (i) added to the polymerization process used to prepare the polymer or due to the polymerization process a component formed, and (ii) a component that remains after the solvent is removed from the polymerization process. In general, the "second polymer composition" is a solvent-free result of the method for preparing the polymer composition and may comprise an oil (softener or extender), a stabilizer, and others (not according to the invention). The component of the polymer. Suitable oils are as defined herein. Other polymers may also be prepared separately in solution, for example in different polymerization reactors, and may be added to the reactor prior to completion of the polymer manufacturing process for the polymer.

The second polymer composition obtained after removing the solvent and the process water from the polymerization process preferably has a Mooney viscosity of at most 150, preferably 20 to 120 and more preferably 30 to 100 (ML 1+4). , 100 ° C, as measured according to ASTM D 1646 (2004) using a Monsanto MV2000 instrument). If the Mooney viscosity of the polymer composition exceeds 150, it may be reflected by the filler incorporation and heat accumulation in the closed mixer, the bundling on the rolling mill, the extrusion rate, the expansion of the extrudate mold, and the smoothness. Machinability may be adversely affected because the compounding machine used by the tire manufacturer is not designed to handle the high Mooney rubber grade and the processing cost is increased. In some cases, Mooney viscosity below 20 can be attributed to increased viscosity and cold flow of the uncrosslinked polymer, which is less preferred, resulting in difficult handling, poor green strength, and poor size during storage. stability. In other cases, a Mooney viscosity of less than 20 may be preferred when the polymer composition is used as a softener, compatibilizer or processing aid in a polymer formulation.

The preferred molecular weight distribution as reflected by the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of the polymer composition obtained after removing the solvent from the polymerization process is from 1.0 to 10.0, preferably from 1.1 to 8.0 and more preferably in the range of 1.2 to 4.5.

In the polymer composition of the first aspect of the invention, the polymers of Formulas 1 and 2 constitute at least 15% by weight, more preferably at least 30% by weight and even more preferably at least 45% by weight of the polymer present. The remaining amount of polymer consists of the other polymers mentioned above. Examples of suitable other polymers are identified in WO 2009/148932 and preferably include styrene-butadiene copolymers, natural rubber, polyisoprene and polybutadiene. These other polymers may be required to have a Mooney viscosity in the range of 20 to 150, preferably 30 to 100 (ML 1+4, 100 ° C, as measured according to ASTM D 1646 (2004)).

The polymer composition of the present invention may also comprise one or more other components added after the polymerization process, including one or more fillers, one or more other polymers other than the polymer of Formula 1 or Formula 2, and one or more crosslinks. Agent (vulcanizing agent) ("third polymer composition"). The polymer composition containing the filler is typically the result of a mechanical mixing process involving the first or second polymer composition of the invention, one or more fillers, and other optional components.

The polymer composition of the present invention may further comprise one or more crosslinkers as further defined below. The polymer composition containing a crosslinking agent can be prepared by kneading the polymer composition of the present invention and one or more crosslinking agents in a kneader at 140 to 180 ° C. The composition optionally comprises one or more components selected from the group consisting of oils, stabilizers, fillers, and other polymers. Alternatively, the polymer composition can be prepared by kneading the polymer composition of the present invention in a kneader at 140 to 180 ° C to form a "first stage" composition. The formation of the "first stage" composition may involve one or more mixing steps, preferably 2 to 7 mixing steps. After cooling, a cross-linking (sulfurizing) agent such as sulfur, a crosslinking (vulcanization) accelerator, optionally zinc oxide and the like are added to the "first stage" composition, and the resulting "second stage" The composition was blended using a Brabender mixer, a Banbury mixer or an open roll mill to form the desired shape.

oil

One or more oils may be used in combination with an uncrosslinked polymer composition comprising components (i) and/or (ii), fillers and/or crosslinkers as appropriate to reduce viscosity or Mooney value or to improve the polymerization. The processability of the composition and the various performance characteristics of the polymer composition once crosslinked.

The oil can be added to the polymer composition after the end of the polymer preparation process and as a separate component after the preparation process. For a representative example and classification of oils, see WO 2009/148932 and US 2005/0159513, each of which is incorporated herein by reference in its entirety.

Representative oils include MES/Mild Extraction Solvate, RAE/Residual Aromatic Extract, including T-RAE/Treated Residual Aromatic Extract and S -RAE), DAE/Distillate Aromatic Extract (TDAE/Treated Distillated Aromatic Extract) and NAP (light and heavy naphthenic oils, including Nytex) 4700, Nytex 8450, Nytex 5450, Nytex 832, Tufflo 2000 and Tufflo 1200). In addition, natural oils including vegetable oils can be used as the extender oil. Representative oils also include functionalized variations of such oils, especially epoxidized or hydroxylated oils. The oils may contain varying concentrations of polycyclic aromatic compounds, paraffin groups, cycloalkyls and aromatics and may have different glass transition temperatures.

Processing aids

Processing aids may optionally be added to the polymer composition. It is usually added to reduce the viscosity. As a result, the mixing period is shortened and/or the number of mixing steps is reduced and, therefore, less energy is consumed and/or a higher throughput during the rubber compound extrusion process is achieved. Representative processing aids are described in Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000 and Werner Kleemann, Kurt Weber, Elastverarbeitung-Kenn Werte und Berechnungsmethoden, Deutscher Verlag für Grundstoffindustrie (Leipzig, 1990), each of which is incorporated herein by reference in its entirety. Examples of representative processing aids include, inter alia: (A) fatty acids including oleic acid, priolene, pristerene and stearic acid; (B) fatty acid salts including Aktiplast GT, PP, ST, T, T-60, 8, F Deoflow S; Kettlitz Dispergator FL, FL Plus; Dispergum 18, C, E, K, L, N, T, R; Polyplastol 6, 15, 19, 21, 23; Struktol A50P, A60, EF44, EF66, EM16, EM50, WA48, WB16, WB42, WS180, WS280 and ZEHDL; (C) dispersant, including Aflux 12, 16, 42, 54, 25; Deoflow A, D; Deogum 80; Deosol H; Kettlitz Dispergator DS, KB, OX Kettlitz-Mediaplast 40, 50, Pertac/GR; Kettlitz-Dispergator SI; Struktol FL and WB 212; and (D) dispersants or processing aids for highly reactive white fillers, including Struktol W33, WB42, HT207, HT254 , HT276; Ultra-Flow 440 and 700S (Performance Additives).

filler

In one embodiment, the polymer composition of the present invention comprises one or more fillers that act as a strengthening agent. Examples of suitable fillers include carbon black (including conductive carbon black), carbon nanotubes (CNT) (including discrete CNTs, hollow carbon fibers (HCF), and modified CNTs carrying one or more functional groups such as hydroxyl, carboxyl, and carbonyl groups. ), graphite, graphene (including discrete graphene flakes), ceria, carbon-ceria double-phase filler, clay (layered niobate, including exfoliated nano-clay and organic clay), calcium carbonate, carbonic acid Magnesium, lignin, amorphous fillers (such as glass particle based fillers, starch based fillers), and combinations thereof. Further examples of suitable fillers are described in WO 2009/148932, which is incorporated herein by reference in its entirety.

Examples of suitable carbon blacks include carbon blacks which are conventionally produced by a furnace process, for example having a nitrogen adsorption specific surface area of 50 to ²⁰⁰ m ² /g and a DBP oil absorption of 80 to 200 ml / 100 g, such as FEF, HAF, ISAF or SAF Category of carbon black, and conductive carbon black. In some embodiments, a high coalescence type carbon black is used. The carbon black is typically used in an amount of 2 to 100 parts by weight or 5 to 100 parts by weight or 10 to 100 parts by weight or 10 to 95 parts by weight per 100 parts by weight of the total polymer.

Examples of suitable cerium oxide fillers include wet cerium oxide, dry cerium oxide, and synthetic cerium oxide type cerium oxide. Cerium oxide having a small particle diameter and a high surface area exhibits a high strengthening effect. The small diameter, high coalescing type of cerium oxide (i.e., having a large surface area and high oil absorption) exhibits excellent dispersibility in the polymer composition, thereby forming excellent workability. In terms of primary particle diameter, the average particle diameter of cerium oxide may be 5 to 60 nm, or 10 to 35 nm. The specific surface area of the cerium oxide particles (measured by the BET method) may be 35 to 300 m ² /g. The cerium oxide is typically used in an amount of 10 to 150 parts by weight or 30 to 130 parts by weight or 50 to 130 parts by weight per 100 parts by weight of the total polymer.

The ceria filler can be used in combination with other fillers including carbon black, carbon nanotubes, carbon-niobium dioxide dual phase fillers, graphene, graphite, clay, calcium carbonate, magnesium carbonate, and combinations thereof.

Carbon black and cerium oxide may be added together, in which case the total amount of carbon black and cerium oxide is 30 to 150 parts by weight or 50 to 150 parts by weight per 100 parts by weight of the total polymer.

The carbon-cerium dioxide dual phase filler is a so-called ceria coated carbon black prepared by coating ceria on a carbon black surface and is marketed under the trademark CRX2000, CRX2002 or CRX2006 (product of Cabot Co.). Commercially available. The carbon-niobium dioxide dual phase filler is added in the same amount as described above for cerium oxide.

Decane coupling agent

In some embodiments, a decane coupling agent (for polymerization) when additionally containing one or more of cerium oxide, a layered cerium salt (such as strontium sulphate) and a carbon-cerium dioxide dual phase filler The compatibilization of the materials and fillers can be added to the polymer composition of the present invention. Typical amounts of decane coupling agent added are from about 1 to about 20 parts by weight, and in some embodiments from about 5 to about 100 parts by weight, based on 100 parts by weight of the total amount of cerium oxide and/or carbon-cerium dioxide dual phase filler. 15 parts by weight.

The decane coupling agent can be classified according to Fritz Röthemeyer, Franz Sommer: Kautschuk Technologie, (Carl Hanser Verlag 2006): (A) difunctionalized decane, including Si230 ((EtO) ₃ Si(CH ₂ ) ₃ Cl), Si225 ((EtO) ₃ SiCH=CH ₂ ), Si263((EtO) ₃ Si(CH ₂ ) ₃ SH), [(EtO) ₃ Si(CH ₂ ) ₃ S _x (CH ₂ ) ₃ Si(OEt) ₃ ] (where x = 3.75 (Si69), 2.35 (Si75) or 2.15 (Si266)), Si264 ((EtO) ₃ Si-(CH ₂ ) ₃ SCN) and Si363 ((EtO)Si((CH ₂ -CH ₂ -O) ₅ (CH ₂ ) ₁₂ CH ₃ ) ₂ (CH ₂ ) ₃ SH)) (Evonic Industries AG); NXT (3-octylthio-1-propyltriethoxydecane), NXT-Z45, NXT-Z100 ( M omentive Performance Materials Inc.); Xiameter® ofs-6030 decane (methacryloxypropyltrimethoxydecane), Xiameter® ofs-6300 decane ((MeO) ₃ SiCH=CH ₂ ), and (B) Monofunctional decanes include Si203 ((EtO) ₃ -Si-C ₃ H ₇ ) and Si208 ((EtO) ₃ -Si-C ₈ H ₁₇ ).

Further suitable examples of decane coupling agents are given in WO 2009/148932 and include bis-(3-hydroxy-dimethyldecyl-propyl) tetrasulfide, bis-(3-hydroxy-dimethyldecyl- Propyl) disulfide, bis-(2-hydroxy-dimethylalkyl-ethyl) tetrasulfide, bis-(2-trans-dimethyl-alkyl-ethyl) disulfide, 3- Hydroxy-dimethyl-alkyl-propyl-N,N-dimethylthioaminemethanyl tetrasulfide and 3-hydroxy-dimethyldecyl-propylbenzothiazole tetrasulfide.

Crosslinker (vulcanizing agent)

Any cross-linking agent conventionally used in the manufacture of rubber products can be used in the present invention, and a combination of two or more than two cross-linking agents can be used.

Sulfur, sulfur compounds that act as sulfur donors, sulfur promoter systems, and peroxides are the most common crosslinking agents. Examples of the sulfur-containing compound serving as a sulfur donor include dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and double-five Methyl thiuram tetrasulfide (DPTT). Examples of the sulfur promoter include an amine derivative, an anthracene derivative, an aldehyde amine condensation product, a thiazole, a thiuram sulfide, a dithiocarbamate, and a thiophosphate. Examples of the peroxide include di-tert-butyl-peroxide, di-(t-butyl-peroxy-trimethyl-cyclohexane), and di-(t-butyl-peroxy-- Isopropyl-)benzene, dichloro-benzylidene peroxide, dicumyl peroxide, tert-butyl-isopropylphenyl-peroxide, dimethyl-di(third) Benzyl-peroxy)hexane, dimethyl-bis(t-butyl-peroxy)hexyne and butyl bis(t-butyl-peroxy)pentanoate (Rubber Handbook, SGF, The Swedish Institution of Rubber Technology 2000).

Additional examples of crosslinkers and additional information can be found in Kirk-Othmer, Encyclopedia of Chemical Technology 3rd Edition, (Wiley Interscience, NY 1982), Vol. 20, pp. 365-468, (specifically, "Vulcanizing Agents" And Auxiliary Materials, pp. 390-402).

A cross-linking accelerator of the thiourethane type, hydrazine type or thiuram type can be used together with the desired crosslinking agent. Adding such as zinc white, cross-linking aid, anti-aging, depending on the situation Other additives for agents, processing adjuvants and the like. The crosslinking agent is typically added to the polymer composition in an amount of from 0.5 to 10 parts by weight per 100 parts by weight of the total polymer or from 1 to 6 parts by weight in some embodiments. Examples of crosslinking accelerators and amounts added to the total polymers are given in WO 2009/148932.

The sulfur accelerator system may or may not contain zinc oxide. Zinc oxide is preferably used as a component of the sulfur promoter system.

Crosslinked polymer composition

The crosslinked polymer composition according to the third aspect of the present invention is obtained by crosslinking a polymer composition of the present invention containing at least one crosslinking agent. Since the crosslinked elastomeric polymer composition of the present invention exhibits low rolling resistance, low dynamic heat buildup, and excellent wet slip performance, it is well suited for use in the manufacture of tires, tire treads, sidewalls, and tire carcasses as well as other industrial products, such as Belts, hoses, vibration dampers and footwear components.

The crosslinked polymer composition is the result of a reactive polymer-polymer crosslink formation process performed on the polymer composition of the present invention containing one or more crosslinkers. The reactive processing converts the substantially uncrosslinked polymer composition into a crosslinked (or vulcanized) polymer composition.

The invention also provides an article comprising at least one component formed from the crosslinked polymer composition of the invention. The article can be a tire, a tire tread, a tire sidewall, an automotive part, a footwear component, a golf ball, a belt, a gasket, a seal, or a hose.

With regard to the manufacture of automotive tires, the following other polymers are of particular interest for use in combination with the polymers of the invention: natural rubber; low cis polybutadiene (LCBR) comprising less than 20% by weight of 1,2-polybutadiene Emulsion SBR (ESBR) and solution SBR (SSBR) rubber having a glass transition temperature above -50 ° C; polybutadiene rubber having a high cis - 1,4-unit content (> 90%), such as by Obtained using a catalyst based on nickel, cobalt, titanium, vanadium, niobium or tantalum; and a polybutadiene rubber having a vinyl content of 0 to 75%; and combinations thereof; having a high trans-1,4-unit content ( >75%) of polybutadiene rubber or containing, for example, between 5% and 45% by weight of styrene and having a high trans-1,4-polybutadiene content in the polybutadiene portion of the copolymer ( >75%) of the SBR (each type of polymer SBR or BR may be obtained from one or more starter compounds comprising an alkaline earth metal compound, such as described in US Patent No. 6,693,160; No. 6,627,715; No. 6,489,415; No. 6,103,842 ; 5,753,579; 5,086,136; and 3,629,213, each of which This is incorporated herein by reference in its entirety; or by the use of a cobalt-based catalyst, such as that described in U.S. Patent No. 6,310,152; 5,834,573; 5,753,761; 5,448,002 and 5,089,574, and U.S. Patent Application The disclosures of each of which is incorporated herein by reference in its entirety, or by the use of a vanadium-based catalyst, such as that described in EP 1 367 069; JP 11301794 and US 3,951,936, each of which is incorporated by reference. This is incorporated herein by reference in its entirety; or by the use of a ruthenium-based catalyst, such as that described in EP 0 964 008, EP 0 924 214, and U.S. Patent No. 6,184,168; No. 6,018,007; No. 4,931,376; No. 5,134,199 And 4,689,368 each of which is incorporated herein by reference in its entirety.

The compositions of the present invention can also be used in the manufacture of high impact polystyrene (HIPS) and butadiene modified acrylonitrile-butadiene-styrene copolymers (ABS) (see, for example, WO 2009/148932, incorporated herein by reference. Into this article).

definition

Alkyl as defined herein (either as such or associated with other groups such as alkaryl or alkoxy) includes straight chain alkyl groups such as methyl (Me), ethyl (Et), n-propyl ( Pr), n-butyl (Bu), n-pentyl, n-hexyl, etc.; branched alkyl groups such as isopropyl, tert-butyl, etc.; and cyclic alkyl groups such as cyclohexyl.

Alkoxy as defined herein includes methoxy (MeO), ethoxy (EtO), propoxy (PrO), butoxy (BuO), isopropoxy, isobutoxy, pentyloxy. Wait.

Aryl groups as defined herein include phenyl, biphenyl and other benzene-like compounds. The aryl group preferably contains only one aromatic ring and most preferably contains a C ₆ aromatic ring.

An aralkyl group as defined herein refers to a combination of one or more aryl groups bonded to one or more alkyl groups, for example, an alkyl-aryl group, an aryl-alkyl group, an alkyl-aryl-alkyl group. And aryl-alkyl-aryl forms. The aralkyl group preferably contains only one aromatic ring and most preferably contains a C ₆ aromatic ring.

Instance

The following examples are provided to further illustrate the invention and are not to be construed as limiting the invention. Examples include the preparation and testing of modified elastomeric polymers; and the preparation and testing of uncrosslinked polymer compositions, and the preparation of crosslinked or cured polymer compositions (also known as vulcanized polymer compositions) and test. All parts and percentages are based on weight unless otherwise stated Expression. "Room temperature" means a temperature of 20 °C. All polymerizations were carried out under a nitrogen atmosphere with the exclusion of moisture and oxygen.

The vinyl content in the polybutadiene portion was measured by FT-IR on a Nicolet AVATAR 360 FT-IR or Nicolet iS 10 FT-IR based on a calibration assay using the ¹ H-NMR method as described above. Determination. An IR sample was prepared using a press.

Bonded styrene content: A calibration curve was prepared by FT-IT (Nicolet AVATAR 360 FT-IR or Nicolet iS 10 FT-IR). An IR sample was prepared using a press. For the IR determination of the bonded styrene in the styrene-butadiene copolymer, four bands were examined: a) for the trans-1,4-polybutadiene unit band at 966 cm ^-1 , b) for the band of cis-1,4-polybutadiene units, c) for the band of the 1,2-polybutadiene units, and d) at 730cm ^-1 in the 700cm 910cm ^{-1 -1} Band for bonded styrene (styrene aromatic bond). The band height is corrected according to the appropriate extinction coefficient and is summarized as a total of 100%. The calibration was carried out via ¹ H- and ¹³ C-NMR (Avance 400 from Bruker Analytik GmbH, ¹ H = 400 MHz; ¹³ C = 100 MHz).

1D NMR spectra were collected on a BRUKER Avance 400 NMR spectrometer (BRUKER Corp.) using a "5 mm dual detection probe". Field uniformity is optimized by maximizing the shackle signal. The sample is shimmed by optimizing the shackle signal. The sample was operated at room temperature (298 K). Deuterated solvents using the following: C ₆ D ₆ ⁽¹ H respect to 7.16ppm; for the ¹³ C-NMR is 128.06ppm), CDCl ₃ (7.26 ppm for ¹ H is; for the ¹³ C-NMR of 77.16ppm), deuterated The signals of the remaining protons of the solvent are each used as an internal reference.

For spectral processing, use the BRUKER TopSpin software. The phasing, baseline correction, and spectral integration of the resulting spectra were performed in a manual mode. See Table 1 for acquisition parameters.

GPC-method: SEC calibrated with narrowly distributed polystyrene standards.

Sample Preparation:

a) Approximately 9-11 mg of dry polymer sample (moisture content < 0.6%) was dissolved in 10 mL of tetrahydrofuran using a 10 mL brown vial. The polymer was dissolved by shaking the vial at 200 u/min for 20 min.

b) The polymer solution was transferred to a 2 ml vial using a 0.45 μm discard filter.

c) The 2 ml vial was placed on a sampler for GPC-analysis.

Dissolution rate: 1.00mL/min

Injection volume: 100.00 μL

The polydispersity (Mw/Mn) is used as a measure of the breadth of the molecular weight distribution. The values of Mw and Mn (weight average molecular weight (Mw) and number average molecular weight (Mn)) were measured by gel permeation chromatography on SEC with refractive index detection (universal calibration). This measurement was carried out in THF at 40 °C. Instrument: Agilent Serie 1100/1200; module settings: degasser, Iso pump, autosampler, thermostat, UV-detector, RI-detector.

In each GPC-device, 4 columns are used in connected mode: 1 × Agilent Plgel 10 μm Guard 50 × 7.5 mm (part number PL1110-1120) plus 3 × Agilent PLgel 10 μm Mixed-B 300 × 7.5 mm (part number PL1110-6100).

GPC standard: EasiCal PS-1 polystyrene standard, spatula A+B (Agilent Technologies, part number PL2010-0505).

Mp1, Mp2 and Mp3 correspond to the (maximum peak) molecular weight measured at the third, second and first peaks of the GPC curve, respectively (peak Mp1 (lowest molecular weight) is located on the right hand side of the curve, and the peak Mp3 (the highest molecular weight) is located on the left hand side of the curve). The maximum peak molecular weight means the molecular weight of the peak at the position of the maximum peak intensity. Mp2 and Mp3 are two or three polymer chains coupled to one macromolecule. Mp1 is a polymer chain (basic molecular weight - two or more than two polymer chains are not coupled to one macromolecule).

The third polymer composition is listed below by a two-stage mixing method. 4. The components in Table 5 or Table 6 were prepared by combining in a 380 ml Banbury mixer (Labstation 350S from Brabender GmbH & Co KG). Stage 1 - In addition to the components of the vulcanization package, all of the components are mixed together to form a Stage 1 formulation. Stage 2 - Mixing the components of the vulcanization package into the Stage 1 formulation to form a Stage 2 formulation.

Mooney viscosity was measured on a MV 2000E from Alpha Technologies UK according to ASTM D 1646 (2004) with a 1 minute warm-up time and a 4 minute rotor operating time at a temperature of 100 °C [ML1+4 (100 °C)]. A rubber Mooney viscosity measurement was performed on the dry (solvent free) original polymer (uncrosslinked rubber). The Mooney values of the original polymers are listed in Table 2.

Measurement of uncrosslinked rheological properties was performed according to ASTM D 5289-95 (reapproved in 2001) using a rotorless shear rheometer (MDR 2000 E from Alpha Technologies UK) to measure cure time (TC) . Rheometer measurements were performed on non-crosslinked second stage polymer formulations according to Table 4, Table 5 or Table 6 at a constant temperature of 160 °C. The amount of polymer sample was about 4.5 g. Sample shape and shape preparation was standardized and defined by the measurement device (MDR 2000 E from Alpha Technologies UK). The TC 50, TC 90 and TC 95 values correspond to the respective times required to achieve 50%, 90% and 95% conversion of the crosslinking reaction. The torque is measured as a function of reaction time. The cross-linking conversion is automatically calculated from the generated torque versus time curve. The TS 1 and TS 2 values are the corresponding times required to increase the torque during cross-linking to 1 dNm and 2 dNm above the corresponding torque minimum (ML).

Tensile strength, elongation at break, and modulus at 300% elongation (modulus 300) were measured on a Zwick Z010 using a Dumbbell C test piece according to ASTM D 412-98A (reapproved in 2002). A standardized dumbbell mold C test piece of 2 mm thickness was used. Tensile strength measurements were performed on cured second stage polymer samples prepared according to Table 4, Table 5 or Table 6 at room temperature. The Stage 2 formulation was crosslinked to TC 95 (95% cross-linking conversion) at 160 ° C in 16-25 minutes (see cure data in Table 7).

Heat build-up was measured on a Doli "Goodrich"-flexometer according to ASTM D 623 Method A. Thermal accumulation measurements were performed on crosslinked second stage polymer samples according to Table 4, Table 5 or Table 6. The Stage 2 formulation was crosslinked to TC 95 (95% cross-linking conversion) at 160 ° C (see cure data in Table 7).

Resilience is measured on Zwick 5109 at 0 ° C and 60 ° C according to DIN 53512 Measurement. This measurement was performed on the cured second stage polymer sample prepared according to Table 4, Table 5 or Table 6. The Stage 2 formulation was crosslinked to TC 95 (95% cross-linking conversion) at 160 ° C plus 5 minutes extra time (see cure data in Table 7). The smaller the index at 0 ° C, the better the slip resistance (lower = better). The higher the index at 60 ° C, the lower the hysteresis loss and the lower the rolling resistance (the higher the better = the better).

DIN wear is measured according to DIN 53516 (1987-06-01). The larger the index, the lower the abrasion resistance (lower = better). Wear measurements were performed on the crosslinked second stage polymer formulation according to Table 4, Table 5 or Table 6.

Using a dynamic mechanical thermal spectrometer "Eplexor 150N" manufactured by Gabo Qualimeter Testanlagen GmbH (Germany), a rectangular sample having a thickness of 2 mm and a width of 10 mm was subjected to tan at 60 ° C by applying 2% dynamic strain at a frequency of 2 Hz at the corresponding temperature. δ and tan δ at 0 °C and tan δ at -10 °C. The starting length of the sample is equal to the clamping distance of the device and is 10 mm. The smaller the index at 60 ° C, the lower the rolling resistance (lower = better). Tan δ at 0 °C and tan δ at -10 °C were measured at 0 °C and -10 °C using the same device and load conditions, respectively. The greater the index at 0 ° C, the better the wet slip resistance and the greater the index at -10 ° C, the better the grip characteristics of the ice (the higher = the better). Tan δ at 60 ° C and tan δ at 0 ° C and tan δ at -10 ° C were measured (see Table 8). The Stage 2 formulation was crosslinked to TC 95 (95% cross-linking conversion) at 160 ° C (see cure data in Table 7). This method resulted in the formation of a visually "no bubble" uniform cured rubber sheet having a thickness of 2 mm. The sample was cut by cutting the iron using a sample having a corresponding width of 10 mm.

In general, the elongation at break, the tensile strength, the modulus 300 and the tan δ at 0 °C, the higher the value of resilience at 60 °C, the better the sample efficiency; the tan δ at 60 ° C, heat accumulation, DIN wear and The lower the resilience at 0 °C, the better the sample performance.

The coefficient of sliding friction is determined by the method according to EN ISO 13287. The measurement was performed with an anti-slip tester (PFI Germany: GSP 3034) with a measurement accuracy better than 2%. The rubber sample was extruded on the metal surface with a defined orthogonal force set to 30 N ± 2% perpendicular to the level surface. The sample was mounted at an angle of 7° to the leveling line to reduce the contact surface between the rubber and the metal and apply the force for 0.2 seconds. The sample was subjected to a force at a determined speed of 0.3 ± 0.03 m/s on the metal surface while measuring the friction force which is the force required to be parallel to the surface and opposite to the direction of movement of the sample. The coefficient of friction is defined as the ratio between the frictional force and the orthogonal force. Along the measurement The route takes about 60 measurement points and calculates the median value of these measurements. The base plate is made of steel No. 1.4371 in accordance with EN 10088-2:2005. The sample was prepared by extruding a rubber sample in the form of 15 x 80 x 115 mm at 200 ° C for 7 minutes at 100 °C. Gloss-treated chrome-plated flakes are used for extrusion with a layer of polyester film foil between the rubber sample and the steel sheet to create a very smooth and uniform surface for the samples. For each material, four samples were prepared and measured.

Compounds P1 and P2 were synthesized and displayed according to the method described in US 4,982,029 and characterized as follows:

¹ H-NMR (300 MHz, 23 ° C, CDCl ₃ ): δ = 7.42 (s, 1H, Ar- H ), 7.30 (s, 7H, Ar- H ), 6.73 (d, 4H, Ar- H ), 5.40 (s, 2H, = C H ₂ ), 5.28 (s, 2H, = C H ₂ ), 2.98 (s, 12H, NC H ₃ ) ppm; ¹³ C-NMR (75 MHz, 23 ° C, CDCl ₃ ) δ = 149.94, 149.70, 141.70, 128.97, 128.46, 127.78, 127.64, 112.20, 111.49, 40.65 ppm.

¹ H NMR (400 MHz, 23 ° C, CDCl ₃ ): δ=7.39-7.40 (m, 1H, ar- H ), 7.35-7.26 (m, 11H, Ar- H ), 5.47 (d, J = 1.2 Hz, 2 H,HC H =C), 5.40 (d, J = 1.2 Hz, 2 H, H CH=C), 1.33 (s, 18H, C(C H ₃ ) ₃ ) ppm; ¹³ C NMR (100 MHz, 23 °C, CDCl ₃ ) δ = 150.74, 149.60, 141.53, 138.18, 128.20, 127.85, 127.75, 125.04, 113.85, 34.54, 31.32 ppm.

Preparation of initiator mixture I1

Compound P1 (34.9 g, 94.9 mmol) and TMEDA (38.7 g, 333 mmol) were dissolved in cyclohexane (286 g) and then n-butyllithium (60.3 g, 190 mmol, 20% by weight solution in cyclohexane) was added. The color of the solution immediately turned dark red, indicating the formation of the dianion DI1 . GC analysis of the I1 sample hydrolyzed with methanol revealed complete conversion of P1 to the corresponding dianion DI1 .

Due to the extremely high air and moisture sensitivity of DI1 , the compound is characterized by its hydrolysate DI1a form. Thus, a sample of the starter mixture was hydrolyzed with excess methanol and characterized by NMR and GC-MS.

¹ H-NMR (400 MHz, 23 ° C, C ₆ D ₆ ): δ = 6.94 - 6.86 (m, 8H, Ar- H ), 6.33 - 6.31 (m, 4H, Ar- H ), 3.63-3.58 (m, 2H, 2x Ar-C H -Ar), 2.22 (s, 12H, NC H ₃ ), 1.82-1.76 (m, 2H, Ar ₂ CH-C H ₂ ), 1.07-0.88 (m, 12H, (CH ) ₂ ) ₃ CH ₃ ), 0.54 (t, 6H, (CH ₂ ) ₃ C H ₃ ) ppm; ¹³ C-NMR (101 MHz, 23 ° C, C ₆ D ₆ ) δ = 149.43, 146.72, 134.07, 128.86, 128.65 , 128.16, 128.15, 127.91, 113.35, 50.99, 40.50, 36.63, 32.34, 28.28, 22.99 ppm.

GC-MS (EI, 70 eV): m/z (%) = 485 (M ⁺ , 22), 413 (M ⁺ -CH ₃ - C ₄ H ₉ , 100), 327 (4), 207 (4), 171 (51), 134 (4).

Preparation of initiator mixture I2

Compound P2 (22.1 g, 56.1 mmol) and TMEDA (22.9 g, 196 mmol) were dissolved in cyclohexane (500 g) and then n-butyl lithium (36.0 g, 112 mmol, 20% by weight solution in cyclohexane) was added. The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I2 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Due to the extremely high air and moisture sensitivity of DI2 , the compound is characterized by its hydrolyzate DI2a form. Thus, a sample of the starter mixture was hydrolyzed with excess methanol and characterized by NMR and GC-MS.

¹ H-NMR (400 MHz, 23 ° C, CDCl ₃ ): δ = 7.28-7.27 (m, 2H, Ar- H ), 7.26-7.24 (m, 2H, Ar- H ), 7.16-7.11 (m, 6H, Ar- H ), 7.02-6.99 (m, 2H, Ar- H ), 3.81 (t, 2H, 2x Ar-C H -Ar), 2.01-1.95 (m, 4H, Ar ₂ CH-C H ₂ ), 1.28 (s, 18H, 2x C(C H ₃ ) ₃ ), 1.27-1.17 (m, 12H, 2x(C H ₂ ) ₃ CH ₃ ), 0.83 (t, 6H, 2x(CH ₂ ) ₃ C H ₃ ) ppm; ¹³ C-NMR (101 MHz, 23 ° C, CDCl ₃ ) δ = 148.59, 145.29, 142.67, 128.40, 127.81, 127.46, 125.69, 125.24, 51.00, 36.02, 34.41, 32.00, 31.49, 27.86, 22.66, 14.20 ppm GC-MS (EI, 70 eV): m/z (%) = 511 (M ⁺ , 5), 439 (M ⁺ -CH ₃ - C ₄ H ₉ , 100), 240 (12), 212 (13), 147(5), 57(11).

Preparation of initiator mixture I3

Compound P2 (31.5 g, 79.8 mmol) and TMEDA (7.43 g, 63.9 mmol) were dissolved in cyclohexane (254 g) and then n-butyllithium (68.2 g, 214 mmol, 20% by weight solution in cyclohexane) was added. . The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I3 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I4

Compound P2 (86.7 g, 109 mmol, 50% by weight solution in cyclohexane) and TMEDA (10.0 g, 87.2 mmol) were dissolved in cyclohexane (91.7 g) and then n-butyllithium (95.5 g, 301 mmol, 20% by weight solution in cyclohexane). The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I4 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I5

Compound P2 (34.2 g, 86.7 mmol), TMEDA (10.4 g, 89.2 mmol), cyclohexane (75.0 g) and n-butyllithium (60.5 g, 186 mmol, 20% by weight solution in cyclohexane) at 40 ° C This was added in this order to a double wall 0.5 liter steel reactor. Immediately after the application of n-butyllithium, the mixture reached 70 °C. The mixture was stirred for 100 min to cool the temperature to 40 °C. GC analysis of a mixture hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 . Additional 1,3-butadiene (45.7 g, 0.84 mol) was added over 10 min. The resulting mixture was used for the polymerization of polymer sample 28.

Preparation of initiator mixture I6

Compound P2 (6.80 g, 8.60 mmol) and TMEDA (0.80 g, 6.90 mmol) were dissolved in cyclohexane (30 g) and then n-butyllithium (7.34 g, 16.7 mmol, 15% by weight solution in cyclohexane) ). The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I6 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I7

Compound P2 (10.0 g, 25.3 mmol) and TMEDA (9.81 g, 88.7 mmol) were dissolved in cyclohexane (150 g) and then n-butyllithium (16.0 g, 50.7 mmol, 20% by weight solution in cyclohexane) ). The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I7 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I8

Compound P2 (4.0 g, 10.1 mmol) and TMEDA (4.16 g, 35.0 mmol) were dissolved in cyclohexane (80 g) and then n-butyllithium (6.39 g, 20.3 mmol, 20% by weight solution in cyclohexane) ). The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I8 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I9

Compound P2 (16.7 g, 42.3 mmol) and TMEDA (17.2 g, 148 mmol) were dissolved in cyclohexane (520 g) and then n-butyllithium (27.0 g, 84.7 mmol, 20% by weight solution in cyclohexane) was added. . The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I9 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Preparation of initiator mixture I10

Compound P2 (16.7 g, 42.3 mmol) and TMEDA (17.2 g, 148 mmol) were dissolved in cyclohexane (520 g) and then n-butyllithium (27.0 g, 84.7 mmol, 20% by weight solution in cyclohexane) was added. . The color of the solution immediately turned dark red, indicating the formation of the dianion DI2 . GC analysis of I10 hydrolyzed with methanol revealed complete conversion of P2 to the corresponding dianion DI2 .

Divinylbenzene (DVB) was purchased from Bowden Chemicals ltd. and used as a 0.16 M solution in cyclohexane. The ratio of the isomers 1,3-DVB/1,4-DVB was 70/30.

Chain end modifier

The chain end modifier E1 is represented by the following formula E1 and synthesized according to the procedure described in WO 2009/148932.

The chain end modifier E2 was purchased from Merck Millipore as 1-methyl-2-pyrrolidone.

The chain end modifier E3 is represented by the following formula E3 and is synthesized as follows: Compound E1 (114 g, 388 mmol) was dissolved in 400 mL of tert-butyl methyl ether (MTBE) and methyl magnesium chloride (140 mL, 420 mmol, tetrahydrofuran) was added via a dropping funnel. 3M solution). After the Grenner reagent was completely added, the mixture was stirred overnight. Methanol (2 mL) was added to hydrolyze a slight excess of the Grignard reagent, followed by filtration to remove the precipitated magnesium salt. All volatiles were removed under reduced pressure and the residue was partially distilled to yield 170 g (79%) of colourless liquid.

¹ H-NMR (400 MHz, 23 ° C, C ₆ D ₆ ): δ = 3.25 (s, 3H, OC H ₃ ), 2.50 (t, 2H, SC H ₂ ), 1.75-1.68 (m, 2H, CH ₂ -C H ₂ -CH ₂ ), 1.00 (s, 9H, C(C H ₃ ) ₃ ), 0.69-0.65 (m, 2H, Si-C H ₂ ), 0.23 (s, 6H, Si (t-Bu) (C H ₃ ) ₂ ), 0.04 (s, 6H, Si(OMe)(C H ₃ ) ₂ ) ppm; ¹³ C-NMR (101 MHz, 23 ° C, C ₆ D ₆ ) δ = 50.02, 30.27, 27.61 , 26.55, 19.14, 15.84, -2.54, -3.39 ppm.

The chain end modifier E4 is represented by the following formula E4 and synthesized according to the procedure described in WO 2009/148932.

Copolymerization of 1,3-butadiene with styrene

Manufacturing Examples 1-111, 14-18, 20-21, 24, 28-34, and 36-39

Copolymerization is carried out in a double-walled 10 liter steel reactor, which is first purged with nitrogen, followed by the addition of an organic solvent, a monomer, a polar coordination compound, a starter compound or His components. The following components were then added in the following order: cyclohexane solvent (4600 grams); butadiene monomer, styrene monomer, tetramethylethylenediamine (TMEDA) and optionally divinylbenzene (DVB) And the mixture was heated to 40 ° C and then titrated with n-butyl lithium to remove traces of moisture or other impurities. The desired polymerization initiator compound is added to the polymerization reactor to initiate the polymerization. If a mixture of starter compounds (e.g., I3 and n-butyllithium in Example 16 in Table 2) is used, the compounds are added simultaneously, unless otherwise stated. The polymerization was carried out for at least 80 minutes, and the polymerization temperature was not allowed to exceed 60 ° C until the monomer was converted to at least 97%. Thereafter, unless otherwise stated, 2.3% of the total amount of butadiene monomer was added, followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was optionally mixed with 27.3% by weight of TDAE oil (VivaTec 500, Hansen & Rosenthal KG), followed by steam stripping for 1 hour to remove solvent and other volatiles, and dried in an oven at 70 ° C. It is then dried for 1 minute to 3 days at room temperature.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing Examples 12, 13, 19 and 22

Copolymerization was carried out in a double wall 40 liter steel reactor which was first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (20200 g); butadiene monomer, styrene monomer, tetramethylethylenediamine (TMEDA) and divinylbenzene (DVB), and the mixture Heat to 40 ° C and then titrate with n-butyl lithium to remove traces of moisture or other impurities. The desired polymerization initiator compound is added to the polymerization reactor to initiate the polymerization. If a mixture of starter compounds (e.g., I3 and n-butyllithium in Example 13 in Table 2) is used, the compounds are added simultaneously, unless otherwise stated. The polymerization was carried out for at least 80 minutes, and the polymerization temperature was not allowed to exceed 60 ° C until the monomer was converted to at least 97%. Thereafter, unless otherwise stated, 2.3% of the total amount of butadiene monomer was added, followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was mixed with 27.3% by weight of TDAE oil (VivaTec 500, Hansen & Rosenthal KG), followed by The solvent and other volatiles were removed by steam stripping for 1 hour and dried in an oven at 70 ° C for 30 minutes and then additionally at room temperature for 1 day to 3 days.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing example 23

Copolymerization was carried out in a double wall 10 liter steel reactor which was first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (4600 g); butadiene monomer, styrene monomer, tetramethylethylenediamine (TMEDA), and the mixture was heated to 40 ° C, followed by positive Butyl lithium is titrated to remove traces of moisture or other impurities. A polymerization initiator I1 is added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 75 minutes without the polymerization temperature exceeding 60 °C. Thereafter, 0.5% of the total amount of butadiene monomer was added, followed by the addition of tin (IV) chloride as a coupling agent. After 10 min, 1.8% of the total butadiene monomer amount was added followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). After the polymer solution is removed from the reactor, a large amount of gelled residue remains around the agitator. The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing Example 26

Copolymerization is carried out in a double-walled 5 liter steel reactor which is first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (2260 g); butadiene monomer, styrene monomer, tetramethylethylenediamine (TMEDA), and divinylbenzene (DVB), and the mixture Heat to 40 ° C and then titrate with n-butyl lithium to remove traces of moisture or other impurities. A polymerization initiator I2 is added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 80 minutes without the polymerization temperature exceeding 60 °C. Thereafter, unless otherwise stated, 2.3% of the total amount of butadiene monomer was added, followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was then stripped with steam for 1 hour to remove solvent and other volatiles, and dried in an oven at 70 ° C for 30 minutes and then additionally at room temperature for 1 day to 3 days.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing Examples 25 and 35

Copolymerization was carried out in a double wall 10 liter steel reactor which was first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (4600 g); butadiene monomer, styrene monomer and tetramethylethylenediamine (TMEDA), and the mixture was heated to 40 ° C, followed by positive Butyl lithium is titrated to remove traces of moisture or other impurities. A polymerization initiator n-butyllithium was added to the polymerization reactor to initiate polymerization. The polymerization was carried out for at least 80 minutes, and the polymerization temperature was not allowed to exceed 60 ° C until the monomer was converted to at least 97%. Thereafter, 0.5% of the total amount of butadiene monomer was added, followed by the addition of a coupling agent. The mixture was stirred for 20 minutes. Subsequently, unless otherwise stated, 1.8% of the total amount of butadiene monomer was added, followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was optionally mixed with 27.3% by weight of TDAE oil (VivaTec 500, Hansen & Rosenthal KG), followed by steam stripping for 1 hour to remove solvent and other volatiles, and dried in an oven at 70 ° C. It is then dried for 1 minute to 3 days at room temperature.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing Example 39

Copolymerization was carried out in a double wall 10 liter steel reactor which was first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (4600 g); butadiene monomer (83% of total butadiene), styrene monomer, tetramethylethylenediamine (TMEDA) and Divinylbenzene (DVB), and the mixture was heated to 40 ° C, followed by titration with n-butyl lithium to remove traces of moisture or other impurities. A polymerization initiator I3 and n-butyllithium were simultaneously added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 100 minutes without the polymerization temperature exceeding 60 °C. Thereafter, 17% of the total amount of butadiene monomer was added and the mixture was further polymerized for 50 min, followed by the addition of a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was mixed with 27.3% by weight of TDAE oil (VivaTec 500, Hansen & Rosenthal KG), followed by steam stripping for 1 hour to remove solvent and other volatiles, and dried in an oven at 70 ° C for 30 minutes and It is then additionally dried at room temperature for 1 day to 3 days.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

Manufacturing example 40

Copolymerization was carried out in a double wall 10 liter steel reactor which was first purged with nitrogen followed by the addition of an organic solvent, monomer, polar coordination compound, starter compound or other components. The following components were then added in the following order: cyclohexane solvent (4600 g); butadiene monomer (83% of total butadiene), styrene monomer (83% of total styrene), Tetramethylethylenediamine (TMEDA) and divinylbenzene (DVB), and the mixture was heated to 40 ° C, followed by titration with n-butyllithium to remove traces of moisture or other impurities. A polymerization initiator I3 and n-butyllithium were simultaneously added to the polymerization reactor to start the polymerization reaction. The polymerization was carried out for 120 minutes without the polymerization temperature exceeding 60 °C. Thereafter, 14.7% of the total butadiene monomer amount and 17% of the total styrene monomer amount were added and the mixture was further polymerized for 60 minutes, followed by addition of 2.3% of the total butadiene monomer amount and 5 minutes thereafter. Add a chain end modifier. After 20 minutes, the polymerization was terminated by the addition of methanol (2 equivalents based on the amount of the starter). To the polymer solution, 2.20 g of IRGANOX 1520 was added as a stabilizer. This mixture was stirred for 10 minutes. The resulting polymer solution was mixed with 27.3% by weight of TDAE oil (VivaTec 500, Hansen & Rosenthal KG), followed by steam stripping for 1 hour to remove solvent and other volatiles, and dried in an oven at 70 ° C for 30 minutes and It is then additionally dried at room temperature for 1 day to 3 days.

The amounts of reagents, the resulting polymer composition, and a number of their properties are summarized in Tables 2 and 3.

The use of the short "-" in the table below indicates that no components have been added. "n.m." indicates that the measurement result has not been obtained, or the corresponding data is not available. If not stated otherwise, n-butyllithium (BuLi) was used as a 20% by weight solution in cyclohexane.

Table 2: Amount of reagent used to prepare an example of the first polymer composition

a BuLi was first added to the polymerization reactor and after 5 min, I3 was added to the reactor, and the concentration of the n-butyllithium solution was 0.159 mol/kg.

b BuLi was first added to the polymerization reactor and after 10 min, I3 was added to the reactor, and the concentration of n-butyllithium solution was 0.159 mol/kg.

c The concentration of n-butyl lithium solution is 0.179mol/kg

d The concentration of n-butyl lithium solution is 0.384mol/kg

^a by SEC

^b vinyl content is the vinyl content of the 1,2-polybutadiene unit content of the final copolymer and is determined by IR spectroscopy

^c styrene content of the final copolymer, and determined by IR spectroscopy

^d The vinyl content of the styrene and 1,2-polybutadiene units in the final copolymer was determined by NMR spectroscopy

^e measured from ungelatinized polymer solution

Polymer composition

The third polymer composition was prepared by combining and compounding the components listed below in Table 4 in a 370 ml Banbury mixer and crosslinking at 200 bar and at 160 ° C in a press vulcanizer. The cross-linking process data and physical properties of each of the composition examples are provided in Tables 7 and 8.

Crosslinked polymer prepared by the same operator under the same conditions on the same day The compositions (as listed in Tables 4, 5, and 6) are identified by capital letters such as A, B, and the like. The first polymer composition contained in the crosslinked polymer composition is reflected by the first polymer composition number (for example, 1, 2, etc.). Thus, there are a series of crosslinked polymer compositions such as 6A, 8A and 11A which can be directly compared to each other.

a phr = the number of parts per 100 parts of rubber based on the total weight of the styrene butadiene copolymer and the high cis 1,4-polybutadiene

b Styron Deutschland GmbH

c Evonic Industries AG

d bis(triethoxydecylpropyl)disulfane, sulfur equivalent per molecule: 2.35

e Cognis GmbH

F- light and ozone-protective wax, Rhein Chemie Rheinau GmbH

g N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, Duslo,as

h Grillo-Zinkoxid GmbH

i VivaTec 500, Hansen & Rosenthal KG

j Solvay AG

k N-t-butyl-2-benzothiazolyl-sulfinamide; Rhein Chemie Rheinau GmbH

l Diphenyl hydrazine, Vulkacit D, Lanxess AG

a phr = the number of parts per 100 parts of rubber based on the total weight of styrene butadiene copolymer (oil-free content) and high cis 1,4-polybutadiene

b Styron Deutschland GmbH

c Evonic Industries AG

d bis(triethoxydecylpropyl)disulfane, sulfur equivalent per molecule: 2.35

e Cognis GmbH

F- light and ozone-protective wax, Rhein Chemie Rheinau GmbH

g N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, Duslo,as

h Grillo-Zinkoxid GmbH

i Solvay AG

j N-t-butyl-2-benzothiazolyl-sulfinamide; Rhein Chemie Rheinau GmbH

k diphenyl fluorene, Vulkacit D, Lanxess AG

a phr = the number of parts per 100 parts of rubber based on the total weight of the styrene butadiene copolymer

b IRB 8, International Reference Carbon Black, Sid Richardson

c Cognis GmbH

d Grillo-Zinkoxid GmbH

e Solvay AG

f N-t-butyl-2-benzothiazolyl-sulfinamide; Rhein Chemie Rheinau GmbH

a modification of the composition of the SSBR polymer, wherein 0 = polymer macromolecule without end modification, 1 = chain end modification at one polymer chain end (according to formula 2), 2 = at the end of two polymer chains The chain end modification (according to Formula 1); the polymer composition of the present invention is represented by 1/2 or 0/1/2.

a modification of the composition of the SSBR polymer, wherein 0 = polymer macromolecule without end modification, 1 = chain end modification at one polymer chain end (according to formula 2), 2 = at the end of two polymer chains The chain end modification (according to Formula 1); the polymer composition of the present invention is represented by 1/2.

It has been found that the polymer composition of the present invention is used in the preparation of crosslinked rubber compositions prepared from unmodified polymer compositions not prepared according to the present invention (see, for example, 11A in Tables 7 and 8). The (intensified cerium oxide or carbon black) polymer composition (see, for example, 6A in Tables 7 and 8) has a relatively reduced tan δ at 60 ° C, a relatively reduced heat buildup, and a relative increase at 60 ° C. Resilience. Surprisingly, it has further been found that the polymer compositions of the present invention exhibit an improved process balance during mechanical mixing with fillers and other ingredients as compared to modified polymer compositions not prepared in accordance with the present invention. Furthermore, the polymer characteristics of the crosslinked polymer composition of the invention measured by tan δ at 0 ° C, tensile strength and elongation at break, especially wet grips, compared to modified polymers not according to the invention The improvement was also made, and the cross-linked polymer composition of the present invention exhibited a rolling resistance, heat accumulation and DIN abrasion resistance at a level of tan δ at 60 °C.

The polymer composition of the present invention can be subjected to the first stage mixing according to Tables 4 to 6 (in which the cerium oxide or carbon black filler and other components are added to the polymer in a mixing step) The second stage of mixing (the mixing step in which the crosslinking agent is added to the polymer composition) is subsequently converted to a crosslinked polymer composition by crosslinking at 160 ° C according to Tables 4 to 6 for 20 min as described herein. . The polymer composition and crosslinked polymer composition (as listed in Tables 4 to 6) prepared by the same operator under the same conditions on the same day were identified by capital letters such as A, B, and the like. The polymer contained in the crosslinked polymer composition is identified by a polymer number (e.g., 6, 8, etc.). Thus, there are a series of crosslinked polymer compositions, such as 6A, 8A, 11A that can be directly compared to one another.

The polymer composition of the present invention has improved processability compared to a polymer composition not according to the present invention, such as a polymer composition comprising substantially only macromolecules modified at both polymer chain ends And a balance between hysteresis loss, wet grip, heat build-up and wear resistance characteristics, where "substantially" means that more than 85% of all polymer chains are modified at both chain ends (ω, ω 'Modification, according to Formula 1), which does not correspond to the present invention.

As shown in Tables 7 and 8, the non-crosslinked, filler-containing material of the present invention is compared to a non-crosslinked polymer composition comprising substantially modified elastomeric macromolecules modified at both polymer chain ends. The Mooney value of the compound of the polymer composition is lowered. The "tensile strength", "elongation at break" and "0°C" of the crosslinked polymer composition comprising the first polymer composition of the present invention compared to the crosslinked polymer composition not prepared according to the present invention The Tan δ" value increases. The reduced Mooney value of the non-crosslinked, filler-containing polymer composition indicates a reduced viscosity resulting in a more economical processing behavior during mechanical mixing of the polymer composition with the filler and other optional components. The increased "tensile strength" and "elongation at break" values result in improved tear strength of the crosslinked polymer composition. The "Tan δ at 0 °C" value is related to the gripping force characteristics on the wetland surface, with higher values corresponding to higher wet grip. Heat accumulation of the crosslinked rubber composition according to the present invention, "rebound at 60 ° C" and "60" compared to a crosslinked polymer composition in which polymer macromolecules are substantially modified at both chain ends The value of Tan δ at °C has not or has not deteriorated significantly. The "heat accumulation" reduction of the salty polymer will improve the durability of the resulting crosslinked polymer composition and correspond to the reduced hysteresis energy loss of the crosslinked polymer composition. In addition, the "heat accumulation" reduction is usually combined with reduced rolling resistance and increased overall elasticity.

In order to demonstrate the benefits of the invention in more detail, some other examples are given.

Example 6 The polymer composition (Tables 2 and 3) prepared by the steps of: Compound P2 is reacted with 2 equivalents of n-butyl to form a dianionic initiator DI2, dianionic initiator which is then used for 1 DI2 Polymerization of 3-butadiene and styrene to obtain a dianion-active styrene-butadiene polymer chain, which is then reacted with a modifier E1 by a ratio of 1:2 modifier to lithium It is modified by a 1:1 mixture of polymer chains modified to produce ω and ω, ω'. This polymer was used to prepare the filler-containing polymer composition 6A of the present invention (Table 7). Example 6A has significantly lower heat buildup, tan δ at 60 °C compared to non-inventive polymer composition 11A comprising a non-modified polymer of the present invention prepared according to the same procedure but without the application of chain end modifier E1 . And increased resilience, tensile strength and elongation at break at 60 ° C (Table 7). Further, the filler-containing polymer composition contains a polymer prepared by the following steps: a) copolymerizing 1,3-butadiene and styrene using a mixed initiator system comprising dianion DI2 and n-butyllithium, And b) modifying the obtained ω,ω'-dianion and ω-monoanionic copolymer chains with a modifier E1 to obtain a mixture of macromolecules modified by ω-(according to formula 2) and ω,ω'- (according to formula 1) (Examples 37 in Table 2 and Table 3). According to Example 37C, the uncrosslinked filler-containing polymer composition (according to Table 5) has a significantly lower ratio than 145.2 of the non-crosslinked polymer composition of Example 12C (according to Table 5). The compound Mooney viscosity was 126.6. The non-inventive polymer composition 12C is based on a non-inventive polymerization prepared by polymerizing 1,3-butadiene and styrene with a dual initiator DI2 and modifying the obtained dianion polymer macromolecule with a modifier E1. Example 12. Thus, the non-inventive polymer 12 essentially comprises a ω,ω' modified polymer chain (according to Formula 1). Considering the slightly degraded tan δ at 60 ° C and the slightly modified tan δ value at 0 ° C (0.536 for Example 37C versus 0.466 for Example 12C), the wet grip/rolling resistance balance of Example 37C was compared to Reference 12C. Still at a similar level. Moreover, the higher tensile strength values and elongation at break values of Example 37C indicate relatively improved mechanical properties of the examples of the present invention.

It is recognized that linear polymer chains have degraded storage stability due to higher cold flow and increased viscosity. Conventionally, the linear polymer chains is at least partially with a metal halide or alkoxide (e.g. _{SnCl 4, Si (OMe) 4} , SiCl 4) coupled to generate star polymer. Examples of the polymer composition 23 that the use of SnCl ₄ as a coupling agent resulting in the polymer chain via a reaction with the reactive chain end having two (ω, ω'- anionic polymer chain ends) of generating significant gelation. Surprisingly, it has further been found that the polymer composition according to the invention has a reduced viscosity which corresponds to a relatively reduced sliding friction coefficient. Examples of the sliding friction coefficient of the non-inventive and inventive polymer compositions are given in Table 9 and Figure 1. The non-inventive polymer composition 38 has a relatively high coefficient of sliding friction of 1.93, while the polymer composition 15 of the invention has a relatively low value of 1.76. A further reduced sliding friction coefficient of 1.60 was found with respect to the polymer composition 19 of the present invention as compared to the polymer compositions 15 and 38, the composition further comprising a coupled polymer chain.

Claims (21)

A polymer composition comprising a modified polymer according to the following formula 1 and formula 2: A ¹ -P ¹ -A ² Formula 1 A ³ -P ² Formula 2 wherein P ¹ and P ² are each independently a polymer chain obtained by anionic polymerization of one or more polymerizable monomers selected from the group consisting of conjugated dienes and aromatic vinyl compounds, wherein each polymer chain P ¹ and P ² contains at least 40% by weight by the total A repeating unit obtained by polymerization of a conjugated diene, and wherein at least anionic polymerization of the polymer chain P ¹ is carried out in the presence of a compound of the following formula 9a: Wherein each R ^{31 is} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl, and (C ₇ -C ₁₈ )aralkyl; each R ³² , R ³³ and R ³⁴ Independently selected from the group consisting of hydrogen, (C ₁ -C ₁₈ )alkyl and (C ₁ -C ₁₈ )alkoxy; each R ^{41 is} independently selected from (C ₁ -C ₁₀₀ )alkyl and (C ₂ -C ₁₀₀ Alkenyl, wherein each R ^{41 is} optionally substituted with one to three (C ₆ -C ₁₂ ) aryl groups and optionally via up to 25 monomer units selected from the group consisting of conjugated dienes and aromatic vinyl compounds The oligomer chain is bonded to the skeleton of the formula 9a, such as 1,3-butadiene and isoprene, and the aromatic vinyl compounds are especially styrene and divinylbenzene. Each M ^{2 is} independently selected from the group consisting of lithium, sodium, and potassium; and k, l, and q are independently selected from the integers of 0, ¹ , ^2, and ³ ; and A ¹ , A ^{2 ,} and A ^{3 are} independently selected from the following formula 3 To Equation 8: Wherein each R ^{1 is} independently selected from (C ₁ -C ₁₆ )alkyl; each R ^{2 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C) ₁₈ ) aralkyl; a and b are independently selected from the integers of 0, 1 and 2, wherein a+b=2; R ^{3 is} independently selected from divalent (C ₁ -C ₁₆ )alkyl, divalent ( C ₆ -C ₁₈ ) aryl, divalent (C ₇ -C ₁₈ ) aralkyl and -R ⁴ -OR ⁵ -, wherein R ⁴ and R ^{5 are} independently selected from divalent (C ₁ -C ₆ ) alkane And Z are independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl, (C ₇ -C ₁₈ )aralkyl, (C=S)-SR ⁶ , wherein R ^{6 is} selected from the group consisting of (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C ₁₈ )Aralkyl; and -M ¹ (R ⁷ ) _c (R ⁸ ) _d , wherein M ¹ is ruthenium or tin, and each R ^{7 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl and (C ₇ -C ₁₈ )aralkyl; each R ⁸ independently Selected from -SR ³ -Si(OR ¹ ) _r (R ² ) _s , wherein R ¹ , R ² and R ³ are as defined above for formula 3, r is independently selected from integers of 1, 2 and 3 and s Is an integer independently selected from 0, 1 and 2, wherein r + s = 3; c is an integer independently selected from 2 and 3; d is an integer independently selected from 0 and 1; and c + d = 3 ; Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₆ )aryl and (C ₇ -C ₁₆ )aralkyl; Wherein each of R ¹³ , R ¹⁴ , R ¹⁸ and R ^{19 is} independently selected from (C ₁ -C ₁₆ )alkyl; R ¹⁵ and R ^{20 are} independently selected from divalent (C ₁ -C ₁₆ )alkyl, divalent (C ₆ -C ₁₈ )aryl, divalent (C ₇ -C ₁₈ ) aralkyl and -R ²⁴ -OR ²⁵ -, wherein R ²⁴ and R ^{25 are} independently selected from divalent (C ₁ -C ₆ ) Alkyl; R ¹⁶ and R ^{17 are} independently selected from (C ₁ -C ₁₆ )alkyl and -SiR ²⁶ R ²⁷ R ²⁸ , wherein R ²⁶ , R ²⁷ and R ^{28 are} independently selected from (C ₁ -C ₁₆ ) An alkyl group, a (C ₆ -C ₁₈ ) aryl group and a (C ₇ -C ₁₈ ) aralkyl group; each of R ²¹ and R ^{22 is} independently selected from (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ And aryl and (C ₇ -C ₁₈ ) aralkyl; each R ^{23 is} independently selected from hydrogen and (C ₁ -C ₆ )alkyl; and f, g, h and i are independently selected from 0, 1 and An integer of 2; f+g=2; and h+i=2; Wherein each of R ²⁹ and R ^{30 is} independently selected from the group consisting of (C ₁ -C ₁₆ )alkyl, (C ₆ -C ₁₈ )aryl, (C ₇ -C ₁₈ )aralkyl, and vinyl; and j is selected from An integer from 1 to 200; and wherein the amount of the polymer of Formula 1 is from 15 mol% to 85 mol% based on the total of the polymer of Formula 1 and the polymer of Formula 2. A polymer composition according to claim 1 which comprises one or more other components selected from the group consisting of (i) added to the polymerization process for preparing the polymers of the formulae 1 and 2 or due to The component formed by the polymerization process, and (ii) the component remaining after the solvent is removed from the polymerization process. The polymer composition of claim 2, wherein the one or more other components are selected from the group consisting of a extender oil, a stabilizer, and other polymers other than the polymer of Formula 1 or Formula 2. The polymer composition of any one of clauses 1 to 3, which comprises one or more components added after the polymerization process, the components being selected from one or more fillers, one or more It is not another polymer of the polymer of Formula 1 or Formula 2 and one or more crosslinking agents. A polymer composition according to claim 4, which comprises one or more crosslinking agents. The polymer composition of any one of clauses 1 to 5, wherein the polymer of the formula 1 and formula 2 constitutes at least 15% by weight of the polymer present. The polymer composition of claim 6, wherein the polymer of the formula 1 and formula 2 constitutes at least 30% by weight, more preferably at least 45% by weight of the polymer present. The polymer composition according to any one of claims 1 to 7, wherein A ¹ , A ² and A ^{3 are} independently selected from the formula 3 as defined in the first item of the patent application. The polymer composition according to any one of claims 1 to 8, wherein in the compound of the formula 9a, M ² is lithium; R ^{41 is} selected from (C ₁ -C ₁₀ )alkyl; each R ³¹ independently selected from hydrogen and (C ₁ -C ₁₀ )alkyl, preferably hydrogen; R ³² and R ³⁴ are the same and selected from hydrogen and (C ₁ -C ₁₈ )alkyl; each R ³³ independently It is selected from the group consisting of hydrogen and (C ₁ -C ₁₈ )alkyl. The polymer composition of any one of clauses 1 to 9, wherein each of P ¹ and P ^{2 is} independently selected from the group consisting of homopolymers of butadiene and isoprene, butadiene and Heterodiene or block copolymers of pentadiene, butadiene and styrene and isoprene and styrene, and random or block terpolymers of butadiene, isoprene and styrene. The application of a polymer composition patentable scope of the items 1 to item 10, wherein the aromatic vinyl monomer constituting these polymers P ¹ and P ² of 2 wt% to 55 wt%. A method of preparing a polymer composition as defined in any one of claims 1 to 11, which comprises the steps of: i) bringing the polymerization initiator mixture to one or more selected from the group consisting of two The polymerizable monomer of the alkene and the aromatic vinyl compound is reacted to obtain a living polymer chain, and the polymerization initiator mixture can be obtained by the following compound of the formula 9: Wherein each R ^{31 is} independently selected from the group consisting of hydrogen, (C ₁ -C ₁₀ )alkyl, (C ₆ -C ₁₂ )aryl, and (C ₇ -C ₁₈ )aralkyl; each R ³² , R ³³ and R ³⁴ Independently selected from the group consisting of hydrogen, (C ₁ -C ₁₈ )alkyl and (C ₁ -C ₁₈ )alkoxy; k, l and q are independently selected from the integers of 0, 1, 2 and 3, and 10 compound obtained by reaction: M ² -R ⁴¹ Formula 10 wherein M ^{2 is} selected from lithium, sodium and potassium and R ^{41 is} selected from (C ₁ -C ₁₀₀ )alkyl and (C ₂ -C ₁₀₀ )alkenyl, each of which R ⁴¹ optionally substituted with one to three (C ₆ -C ₁₂ ) aryl groups and optionally via oligomeric chain bonds consisting of up to 25 monomer units selected from the group consisting of conjugated dienes and aromatic vinyl compounds To the M ² , the conjugated dienes are especially 1,3-butadiene and isoprene, and the aromatic vinyl compounds are especially styrene and divinyl benzene; wherein the active polymer chains a repeating unit obtained by polymerization of at least 40% by weight of the conjugated diene, wherein the molar ratio of the compound of the formula 10 to the compound of the formula 9 is in the range of 1:1 to 8:1, and ii) the step i And the chain end modification of the one or more compounds selected from the group consisting of the following formulas 11 to 15 Agent reaction: Wherein R ¹ , R ² , R ³ , Z, r and s are as defined in the first aspect of the patent application; Wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} as defined in the first aspect of the patent application; Wherein R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^{17 are} as defined in formula 1 in relation to formula 6; t is an integer selected from 1, 2 and 3; u is selected from 0, 1 and 2 An integer; and t+u=3; Wherein ^{R 18, R 19, R 20} , R 21, R 22 and R ²³ as patent application on the scope of formula 1 in which seven defined; V is selected from an integer of 1, 2 and 3; W is selected from 0, An integer of 1 and 2; and v+w=3; Wherein each of R ²⁹ and R ^{30 is} as defined in Formula 1 in Claim 1; and x is an integer selected from 1 to 6; and wherein the chain end modifiers of Formula 11 to Formula 15 are used in the following amounts: (i) when the molar ratio of the compound of the formula 10 to the compound of the formula 9 is in the range of 1:1 to 2.1:1, 0.15 to 0.85 moles per mole of the compound of the formula 10, and (ii) when the compound of the formula 10 and the formula 9 The molar ratio of the compound is from 0.5 to 3 moles per mole of the compound of the formula 10 when it is in the range of from greater than 2.1:1 to 8:1. The method of claim 12, wherein in the compound of formula 9, each R ^{31 is} independently selected from the group consisting of hydrogen and (C ₁ -C ₁₀ )alkyl, preferably hydrogen; and R ³² and R ³⁴ are the same. And selected from hydrogen and (C ₁ -C ₁₈ )alkyl; each R ^{33 is} independently selected from hydrogen and (C ₁ -C ₁₈ )alkyl; and in the compound of formula 10, M ² is lithium; and R ⁴¹ It is selected from (C ₁ -C ₁₀ )alkyl. The method of claim 12 or 13, wherein the molar ratio between the compound of the formula 10 and the compound of the formula 9 is in the range of 1.5:1 to 8:1, preferably 2:1 to 6:1. Inside. The method of any one of clauses 12 to 14, wherein the molar ratio of the compound of formula 10 to the compound of formula 9 is greater than 2.1:1 to 7:1, preferably 2.1:1 to 6 :1, more preferably in the range of 2.5:1 to 3.5:1, even more preferably approximately 3:1. The method of any one of clauses 12 to 15, wherein the one or more chain end modifiers are selected from the group consisting of the compound of formula 11 as defined in claim 11 of the patent application. The method of any one of claims 12 to 16, wherein one or more selected from the group consisting of a randomizer and a coupling agent are added. The method of claim 17, wherein the coupling agent is divinylbenzene. A crosslinked polymer composition by as defined in item 5 of the scope of the patent application The polymer composition is obtained by crosslinking. An article comprising at least one component formed from a crosslinked polymer composition as defined in claim 19 of the scope of the patent application. Articles of claim 20, which are tires, tire treads, tire sidewalls, automotive parts, footwear components, golf balls, belts, gaskets, seals or hoses.